CN113817092A - Preparation method and device of high-content acrylic copolymer - Google Patents
Preparation method and device of high-content acrylic copolymer Download PDFInfo
- Publication number
- CN113817092A CN113817092A CN202111129203.7A CN202111129203A CN113817092A CN 113817092 A CN113817092 A CN 113817092A CN 202111129203 A CN202111129203 A CN 202111129203A CN 113817092 A CN113817092 A CN 113817092A
- Authority
- CN
- China
- Prior art keywords
- pipe
- acrylic copolymer
- reaction
- cylinder
- reaction cylinder
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229920006243 acrylic copolymer Polymers 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 56
- 238000003756 stirring Methods 0.000 claims abstract description 42
- 238000001816 cooling Methods 0.000 claims abstract description 28
- 239000007788 liquid Substances 0.000 claims abstract description 28
- 239000002994 raw material Substances 0.000 claims abstract description 26
- 239000000178 monomer Substances 0.000 claims abstract description 24
- 238000010438 heat treatment Methods 0.000 claims abstract description 19
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 13
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims abstract description 13
- 239000011259 mixed solution Substances 0.000 claims abstract description 13
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims abstract description 13
- 239000007787 solid Substances 0.000 claims abstract description 13
- 239000002904 solvent Substances 0.000 claims abstract description 13
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims abstract description 5
- 239000003999 initiator Substances 0.000 claims abstract description 5
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 3
- 239000000047 product Substances 0.000 claims description 29
- 238000007789 sealing Methods 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 16
- 238000007599 discharging Methods 0.000 claims description 14
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 12
- 239000013078 crystal Substances 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 12
- 239000012467 final product Substances 0.000 claims description 12
- 239000001632 sodium acetate Substances 0.000 claims description 12
- 235000017281 sodium acetate Nutrition 0.000 claims description 12
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 11
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 11
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 5
- 229920002126 Acrylic acid copolymer Polymers 0.000 claims description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 3
- 238000009434 installation Methods 0.000 claims description 3
- UIIIBRHUICCMAI-UHFFFAOYSA-N prop-2-ene-1-sulfonic acid Chemical compound OS(=O)(=O)CC=C UIIIBRHUICCMAI-UHFFFAOYSA-N 0.000 claims description 3
- 229920000536 2-Acrylamido-2-methylpropane sulfonic acid Polymers 0.000 claims description 2
- XHZPRMZZQOIPDS-UHFFFAOYSA-N 2-Methyl-2-[(1-oxo-2-propenyl)amino]-1-propanesulfonic acid Chemical compound OS(=O)(=O)CC(C)(C)NC(=O)C=C XHZPRMZZQOIPDS-UHFFFAOYSA-N 0.000 claims description 2
- 230000005540 biological transmission Effects 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 238000005265 energy consumption Methods 0.000 abstract description 3
- 238000012546 transfer Methods 0.000 abstract description 3
- 230000005764 inhibitory process Effects 0.000 description 11
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 10
- 238000007334 copolymerization reaction Methods 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 8
- 229920000642 polymer Polymers 0.000 description 8
- 239000000376 reactant Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 229920001577 copolymer Polymers 0.000 description 7
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 6
- DZSVIVLGBJKQAP-UHFFFAOYSA-N 1-(2-methyl-5-propan-2-ylcyclohex-2-en-1-yl)propan-1-one Chemical compound CCC(=O)C1CC(C(C)C)CC=C1C DZSVIVLGBJKQAP-UHFFFAOYSA-N 0.000 description 5
- 229910000019 calcium carbonate Inorganic materials 0.000 description 5
- 238000011161 development Methods 0.000 description 5
- 239000006185 dispersion Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 239000002455 scale inhibitor Substances 0.000 description 4
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 3
- JHUFGBSGINLPOW-UHFFFAOYSA-N 3-chloro-4-(trifluoromethoxy)benzoyl cyanide Chemical compound FC(F)(F)OC1=CC=C(C(=O)C#N)C=C1Cl JHUFGBSGINLPOW-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 2
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 230000000149 penetrating effect Effects 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 2
- 238000002834 transmittance Methods 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 229910052925 anhydrite Inorganic materials 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- 229910000389 calcium phosphate Inorganic materials 0.000 description 1
- 235000011010 calcium phosphates Nutrition 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005485 electric heating Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000000413 hydrolysate Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Images
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
- C08F220/04—Acids; Metal salts or ammonium salts thereof
- C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/18—Stationary reactors having moving elements inside
-
- 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
- C08F220/52—Amides or imides
- C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
- C08F220/58—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing oxygen in addition to the carbonamido oxygen, e.g. N-methylolacrylamide, N-(meth)acryloylmorpholine
- C08F220/585—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing oxygen in addition to the carbonamido oxygen, e.g. N-methylolacrylamide, N-(meth)acryloylmorpholine and containing other heteroatoms, e.g. 2-acrylamido-2-methylpropane sulfonic acid [AMPS]
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention provides a preparation method of a high-content acrylic copolymer, which comprises the following steps: s1: putting a mixed solution of an acrylic monomer and an unsaturated monomer containing sulfonic acid in a molar ratio of 1: 1-10: 1 into a reaction kettle, adding sodium bisulfite according to 1-15% of the mass of a monomer raw material, heating to 60-95 ℃, then dropwise adding an initiator of 2-15% of the total mass of the monomer raw material, and carrying out polymerization reaction for 6-8 hours to obtain a light yellow to amber transparent liquid; s2: concentrating the product obtained from the S1 at the temperature of 80-100 ℃ for 6-12 h to obtain a yellowish to amber viscous liquid, wherein the solid content is controlled at 60-80%; s3: and (4) adding a solvent absolute ethyl alcohol into the product obtained in the step (S2), cooling to 40-60 ℃, and continuously stirring for 2-3 hours. The preparation method and the device of the high-content acrylic copolymer provided by the invention can be used for producing the crystalline product of the acrylic copolymer, have the advantages of simple package, reduced storage and transportation energy consumption in flow transfer, easy control of field application and the like, and bring great convenience to product use.
Description
Technical Field
The invention relates to the field of chemical treatment, in particular to a preparation method and a device of a high-content acrylic copolymer.
Background
The copolymer dispersion scale inhibitor is a novel water treatment agent developed before and after 80 years, has excellent performance and plays an important role in the development of phosphorus-series and molybdenum-series water treatment technologies. The development and application of the method lead the water treatment technology to be a great step forward and become a hot spot for the development and development of water treatment agents at home and abroad.
Among the numerous developed copolymer dispersion scale inhibitors, the acrylic acid-sulfonate copolymer attracts general attention due to its excellent performance, and the development has been hot at home and abroad.
However, the existing acrylic acid-sulfonate copolymer is liquid, and has the defects of difficult packaging, high consumption of storage and transportation energy in circulation, complex field application, difficult control and the like, thereby causing great waste.
Therefore, it is necessary to provide a method and an apparatus for preparing a high-content acrylic copolymer to solve the above problems.
Disclosure of Invention
The invention provides a preparation method and a device of a high-content acrylic copolymer, which solve the problems of difficult packaging, high storage and transportation energy consumption in flow transfer due to the fact that the conventional acrylic acid-sulfonate copolymer is usually liquid.
In order to solve the technical problems, the preparation method of the high-content acrylic copolymer provided by the invention comprises the following steps:
s1: putting a mixed solution of an acrylic monomer and an unsaturated monomer containing sulfonic acid in a molar ratio of 1: 1-10: 1 into a reaction kettle, adding sodium bisulfite according to 1-15% of the mass of a monomer raw material, heating to 60-95 ℃, then dropwise adding an initiator of 2-15% of the total mass of the monomer raw material, and carrying out polymerization reaction for 6-8 hours to obtain a light yellow to amber transparent liquid;
s2: concentrating the product obtained from the S1 at the temperature of 80-100 ℃ for 6-12 h to obtain a yellowish to amber viscous liquid, wherein the solid content is controlled at 60-80%;
s3: adding solvent absolute ethyl alcohol into the product obtained in the step S2, cooling to 40-60 ℃, and continuously stirring for 2-3 hours;
s4: and (5) adding crystal nucleus sodium acetate into the product obtained in the step S3, cooling, crystallizing, centrifugally dewatering and drying to obtain the final product.
Preferably, the sulfonic acid-containing unsaturated monomer in S1 is 2-acrylamido-2-methylpropanesulfonic acid and salts thereof or allylsulfonic acid and salts thereof.
Preferably, the initiator in S1 is sodium persulfate, ammonium persulfate, or hydrogen peroxide.
The present invention also provides a preparation apparatus for a high-content acrylic copolymer, comprising:
the reaction barrel comprises an outer barrel and an inner barrel, the inner barrel is fixed in the outer barrel, and a gas conducting cavity is formed between the outer barrel and the inner barrel;
the stirring part comprises a rotating pipe, the top end of the rotating pipe penetrates through the inner cylinder and extends into the air guide cavity, the top end of the rotating pipe is communicated with the inside of the air guide cavity, a stirring blade is fixedly connected to the surface of the rotating pipe and positioned in the reaction cylinder, and the stirring inside is communicated with the inside of the rotating pipe;
the rotary driving piece is connected to the bottom end of the rotating pipe and is positioned outside the reaction cylinder;
the driving piece is fixedly arranged at the bottom of the reaction cylinder and is in transmission connection with the rotary driving piece;
the temperature adjusting pipe is connected to the mounting pipe on one side of the reaction cylinder.
Preferably, the temperature adjusting pipe fitting comprises a three-way pipe, two ends of the three-way pipe are both connected with L-shaped pipes, one ends of the two L-shaped pipes are respectively connected with a cooling pipe and a hot air pipe, and valves are mounted on the two L-shaped pipes.
Preferably, the rotary driving part comprises a connecting pipe, the connecting pipe is connected to the bottom end of the rotating pipe, the bottom end of the connecting pipe is connected with a rotary connector, and one end of the rotary connector is connected with an exhaust pipe.
Preferably, the driving piece comprises a mounting frame, the mounting frame is fixed to the bottom of the reaction cylinder, a motor is fixedly mounted at the bottom of the mounting frame, one end of the motor output shaft is fixedly connected with a rotating shaft through a coupler, and a driving gear is fixedly connected to the surface of the rotating shaft.
Preferably, the driving gear is engaged with the driven gear.
Preferably, the bottom of the reaction cylinder is connected with an annular discharge pipe, the annular discharge pipe is in threaded connection with a sealing cover, the sealing cover comprises an annular cover, and a sealing plug is mounted inside the annular cover.
Preferably, a feeding pipe is installed at the top of the reaction cylinder, and a temperature sensor is installed on the reaction cylinder.
Compared with the related technology, the preparation method and the device of the high-content acrylic copolymer provided by the invention have the following beneficial effects:
the invention provides a preparation method of a high-content acrylic copolymer, which can produce a crystallized product of the acrylic copolymer, has simple package, reduces the storage and transportation energy consumption in flow transfer, is easy to control field application and the like, and brings great convenience to product use.
Drawings
FIG. 1 is a schematic structural view of a preferred embodiment of an apparatus for preparing a high-content acrylic copolymer according to the present invention;
FIG. 2 is a schematic structural view of the reaction cartridge shown in FIG. 1;
FIG. 3 is a schematic view of the configuration of the stirring member shown in FIG. 1;
FIG. 4 is a schematic view of the seal cap shown in FIG. 1;
FIG. 5 is a schematic view of the pod of FIG. 1;
FIG. 6 is a schematic structural view of a twelfth embodiment of an apparatus for preparing a high content acrylic copolymer according to the present invention;
fig. 7 is a schematic view of the structure of the guide member shown in fig. 6.
Reference numbers in the figures:
1. a reaction cylinder 101, an outer cylinder 102, an inner cylinder 103, an air guide cavity,
2. a stirring piece 21, a rotating pipe 22 and a stirring blade,
3. a rotary driving piece 31, a connecting pipe 32, a rotary connector 33, an exhaust pipe 34, a driven gear,
4. a driving piece 41, a mounting frame 42, a motor 43 and a driving gear,
5. a temperature adjusting pipe fitting 51, a three-way pipe 52, an L-shaped pipe 53, a cold air pipe 54, a hot air pipe 55 and a valve,
6. an annular discharge pipe is arranged on the upper portion of the discharge pipe,
7. a sealing cover, 71, an annular cover, 72, a sealing plug,
8. a guide cover 9, a temperature sensor 10, an installation pipe 11, an air inlet hole 12, a driving plate 13, an extension pipe 14, an extension rod 15 and a guide piece,
211. upper end pipe, 212, lower end pipe.
Detailed Description
The invention is further described with reference to the following figures and embodiments.
The first embodiment:
putting a mixed solution of acrylic monomers and 2-acrylamide-2-methylpropanesulfonic acid in a molar ratio of 1:1 into a reaction kettle, adding sodium bisulfite accounting for 2% of the mass of the raw materials, heating to 75 ℃, then dropwise adding sodium persulfate accounting for 5% of the total mass of the raw materials, and carrying out copolymerization reaction for 6 hours to obtain a light yellow to amber transparent liquid; concentrating the product at 95 deg.C for 8h to obtain yellowish to amber viscous liquid with solid content controlled at 80%; adding solvent anhydrous ethanol into the obtained product, cooling to 45 ℃, and continuously stirring for 2 h; then adding crystal nucleus sodium acetate, and cooling and crystallizing; dehydrating; and drying to obtain the final product.
Second embodiment:
putting a mixed solution of acrylic monomers and 2-acrylamide-2-methylpropanesulfonic acid in a molar ratio of 2:1 into a reaction kettle, adding sodium bisulfite according to 5% of the mass of raw materials, heating to 70 ℃, then dropwise adding sodium persulfate accounting for 8% of the total mass of the raw materials, and carrying out copolymerization reaction for 6 hours to obtain a light yellow to amber transparent liquid; concentrating the product at 90 deg.C for 10h to obtain yellowish to amber viscous liquid with solid content controlled at about 75%; adding solvent anhydrous ethanol into the obtained product, cooling to 50 ℃, and continuously stirring for 3 hours; then adding crystal nucleus sodium acetate, and cooling and crystallizing; dehydrating; and drying to obtain the final product.
The third embodiment:
putting a mixed solution of acrylic acid monomers and 2-acrylamide-2-methyl propyl sodium sulfonate in a molar ratio of 3:1 into a reaction kettle, adding sodium bisulfite according to 5% of the mass of raw materials, heating to 80 ℃, then dropwise adding sodium persulfate accounting for 10% of the total mass of the raw materials, and carrying out copolymerization reaction for 5 hours to obtain a light yellow to amber transparent liquid; concentrating the product at 90 deg.C for 10h to obtain yellowish to amber viscous liquid with solid content controlled at 70%; adding solvent anhydrous ethanol into the obtained product, cooling to 40 ℃, and continuously stirring for 3 hours; then adding crystal nucleus sodium acetate, and cooling and crystallizing; dehydrating; and drying to obtain the final product.
Fourth embodiment 4:
putting a mixed solution of acrylic acid monomers and 2-acrylamide-2-methylpropanesulfonic acid in a molar ratio of 4:1 into a reaction kettle, adding sodium bisulfite according to 6% of the mass of raw materials, heating to 75 ℃, then dropwise adding sodium persulfate accounting for 8% of the total mass of the raw materials, and carrying out copolymerization reaction for 6 hours to obtain a light yellow to amber transparent liquid; concentrating the product at 95 deg.C for 6h to obtain yellowish to amber viscous liquid with solid content controlled at 75%; adding solvent anhydrous ethanol into the obtained product, cooling to 45 ℃, and continuously stirring for 2 h; then adding crystal nucleus sodium acetate, and cooling and crystallizing; dehydrating; and drying to obtain the final product.
Fifth embodiment:
putting a mixed solution of acrylic acid monomers and 2-acrylamide-2-methylpropanesulfonic acid in a molar ratio of 4:1 into a reaction kettle, adding sodium bisulfite according to 10% of the mass of raw materials, heating to 85 ℃, then dropwise adding sodium persulfate accounting for 12% of the total mass of the raw materials, and carrying out copolymerization reaction for 5 hours to obtain a light yellow to amber transparent liquid; concentrating the product at 95 deg.C for 8h to obtain yellowish to amber viscous liquid with solid content controlled at 75%; adding solvent anhydrous ethanol into the obtained product, cooling to 45 ℃, and continuously stirring for 3 hours; then adding crystal nucleus sodium acetate, and cooling and crystallizing; dehydrating; and drying to obtain the final product.
Sixth embodiment:
putting a mixed solution of acrylic acid monomers and allyl sulfonic acid in a molar ratio of 5:1 into a reaction kettle, adding sodium bisulfite according to 6% of the mass of the raw materials, heating to 90 ℃, then dropwise adding ammonium persulfate accounting for 15% of the total mass of the raw materials, and carrying out copolymerization reaction for 5 hours to obtain a light yellow to amber transparent liquid; concentrating the product at 80 deg.C for 12h to obtain yellowish to amber viscous liquid with solid content controlled at 75%; adding solvent anhydrous ethanol into the obtained product, cooling to 50 ℃, and continuously stirring for 3 hours; then adding crystal nucleus sodium acetate, and cooling and crystallizing; dehydrating; and drying to obtain the final product.
Seventh embodiment:
putting a mixed solution of acrylic acid monomers and sodium allylsulfonate in a molar ratio of 5:1 into a reaction kettle, adding sodium bisulfite according to 8% of the mass of raw materials, heating to 95 ℃, then dropwise adding sodium persulfate accounting for 15% of the total mass of the raw materials, and carrying out copolymerization reaction for 8 hours to obtain light yellow to amber transparent liquid; concentrating the product at 100 deg.C for 6h to obtain yellowish to amber viscous liquid with solid content controlled at 80%; adding solvent anhydrous ethanol into the obtained product, cooling to 45 ℃, and continuously stirring for 3 hours; then adding crystal nucleus sodium acetate, and cooling and crystallizing; dehydrating; and drying to obtain the final product.
Eighth embodiment:
putting a mixed solution of acrylic acid monomers and 2-acrylamide-2-methylpropanesulfonic acid in a molar ratio of 9:1 into a reaction kettle, adding sodium bisulfite according to 3% of the mass of raw materials, heating to 80 ℃, then dropwise adding sodium persulfate accounting for 12% of the total mass of the raw materials, and carrying out copolymerization reaction for 6 hours to obtain a light yellow to amber transparent liquid; concentrating the product at 85 deg.C for 12h to obtain yellowish to amber viscous liquid with solid content controlled at 75%; adding solvent anhydrous ethanol into the obtained product, cooling to 40 ℃, and continuously stirring for 3 hours; then adding crystal nucleus sodium acetate, and cooling and crystallizing; dehydrating; and drying to obtain the final product.
Ninth embodiment:
putting a mixed solution of acrylic acid monomers and 2-acrylamide-2-methyl propyl sodium sulfonate in a molar ratio of 10:1 into a reaction kettle, adding sodium bisulfite according to 6% of the mass of raw materials, heating to 85 ℃, then dropwise adding sodium persulfate accounting for 15% of the total mass of the raw materials, and carrying out copolymerization reaction for 6 hours to obtain a light yellow to amber transparent liquid; concentrating the product at 90 deg.C for 10h to obtain yellowish to amber viscous liquid with solid content controlled at 75%; adding solvent anhydrous ethanol into the obtained product, cooling to 45 ℃, and continuously stirring for 3 hours; then adding crystal nucleus sodium acetate, and cooling and crystallizing; dehydrating; and drying to obtain the final product.
Tenth embodiment:
putting a mixed solution of acrylic acid monomers and sodium allylsulfonate with a molar ratio of 10:1 into a reaction kettle, adding sodium bisulfite according to 5% of the mass of raw materials, heating to 95 ℃, then dropwise adding sodium persulfate accounting for 15% of the total mass of the raw materials, and carrying out copolymerization reaction for 8 hours to obtain light yellow to amber transparent liquid; concentrating the product at 90 deg.C for 12h to obtain yellowish to amber viscous liquid with solid content controlled at 80%; adding solvent anhydrous ethanol into the obtained product, cooling to 45 ℃, and continuously stirring for 3 hours; then adding crystal nucleus sodium acetate, and cooling and crystallizing; dehydrating; and drying to obtain the final product.
The scale inhibition performance test conditions and test results of the polymer are as follows:
and (3) testing conditions are as follows:
and (3) measuring the scale inhibition calcium carbonate performance of the sample by using a static scale inhibition method. The test water is the preparation water:
500mL of a water sample (pH = 9) containing a drug at a certain mass concentration, rho (Ca2+) =600mg/L, rho (HCO3-) =500mg/L, rho (CO32-) =100mg/L (both calculated as CaCO 3) was put into a volumetric flask, and the flask was kept at a constant temperature for 10 hours in a water bath at (50. + -.1) ° C, then taken out, cooled, filtered, and the Ca2+ content of the filtrate was measured, and a blank experiment was conducted.
The experimental method for the performance of the scale inhibition Ca3 (PO 4) 2 is similar to the method for measuring the performance of the scale inhibition calcium carbonate, but the initial ion mass concentration is as follows: ρ (Ca2+) =250mg/L, ρ (PO43-) =5 mg/L.
The experimental method for the performance of the CaSO4 scale inhibitor is similar to the method for measuring the performance of the calcium carbonate scale inhibitor, but the initial ion mass concentration is as follows: ρ (Ca2+) =2500mg/L, ρ (SO42-) =7200 mg/L.
The experimental method for the performance of the scale inhibition Zn (OH) 2 is similar to the method for measuring the performance of the scale inhibition calcium carbonate, but the initial ion mass concentration is as follows: ρ (Ca2+) =250mg/L, ρ (Zn2+) =5mg/L, ρ (HCO3-) =250 mg/L.
Test results
When the dosage of the polymer reaches 5mg/L, the calcium carbonate scale inhibition capacity reaches 79.5%.
When the dosage of the polymer reaches 8mg/L, the calcium phosphate scale inhibition capacity reaches 92.5%.
When the dosage of the polymer reaches 10mg/L, the calcium sulfate scale inhibition capacity of the polymer reaches nearly 100 percent.
When the dosage of the polymer reaches 8mg/L, the zinc scale inhibition capacity of the polymer reaches 89.5 percent.
The test conditions and test results of the dispersed iron oxide performance evaluation are as follows:
test conditions of the performance of the dispersed iron oxide are as follows:
the initial ion concentrations were: ρ (Ca2+) =250mg/L, ρ (Fe2+) =10mg/L (formulated with FeSO4 · 7H 2O), pH =9, reaction temperature 50 ℃, reaction time 5H. The hydrolysate of FeSO4 & 7H2O was used as an iron oxide suspension medium, heated in a water bath, cooled, and then allowed to stand, and the supernatant was collected and measured for light transmittance by a 721 spectrophotometer.
And (3) testing results:
when the dosage of the polymer reaches 5mg/L, the dispersion effect is optimal, the light transmittance is 73.5%, the dosage of the copolymer is continuously increased, and the dispersion effect is not greatly changed. The copolymer of the invention has better dispersing ability, and the formed scale is softer and is easy to be washed away by water.
Eleventh embodiment
Please refer to fig. 1, fig. 2, fig. 3, fig. 4 and fig. 5 in combination. The preparation device of the high-content acrylic copolymer comprises: the reaction cylinder 1 used for reaction, the reaction cylinder 1 includes inner cylinder 102 and outer cylinder 101, leave the air guide cavity 103 between inner cylinder 102 and outer cylinder 101, when reacting, when needing to heat up, can be through leading-in the inside of the air guide cavity 103 with the hot gas flow, the hot gas flow is through leading-in the inside of the whole reaction cylinder 1, increase in the contact area of the reactant, raise the heating rate, when leading-in the cold air like this, raise the speed of cooling crystallization, the inner cylinder 102 of the reaction cylinder 1 is the metal material support with good heat conductivity, the outside of the outer cylinder 101 has insulating layers, reduce the loss of the heat;
the reaction tube 1 is provided with a mounting tube 10 on one side, the mounting tube 10 is connected with a temperature adjusting tube 5 for inputting hot air and cold air, when hot air flow is needed to be introduced, a valve 55 on the hot air tube 54 is opened, the hot air enters the air guide cavity 103 through the hot air tube 54 via a three-way pipe 51, similarly, when cold air is input, the valve 55 on the cold air tube 53 is opened, wherein one end of the hot air tube is connected to a heating device, an electric heating resistance wire is arranged in the heating device, the other end of the heating device is connected with a fan through a pipeline, one end of the cold air tube 53 is connected with an output end provided with a refrigerating device, the refrigerating device can be an air conditioner and the like, when the air conditioner is arranged in a box body, and the box body is provided with an air outlet pipe connected with the cold air tube 53.
The reaction cylinder 1 is internally provided with a stirring part 2, the stirring part 2 comprises a rotating pipe 21, the surface of the rotating pipe 21 is connected with a plurality of groups of stirring blades 22 for stirring, preferably four stirring blades 22 are arranged in each group, the inside of each stirring blade 22 is provided with a cavity and is communicated with the rotating pipe 21, after airflow enters the air guide cavity 103, the airflow enters the rotating pipe 21 so as to be filled into the stirring blades 22, (wherein the stirring blades 22 and the rotating pipe 21 are made of metal materials with good heat conductivity), the reactant is heated or cooled through the stirring blades 22, the contact area between the stirring blades and the reactant is greatly increased by rotation, so that the reaction can be rapidly heated or cooled, the penetrating part between the upper end of the rotating pipe 21 and the inner cylinder 102 is mechanically sealed, the outer side of the top end is provided with a flange, and the whole rotating pipe 21 can be supported and limited;
the bottom end of the rotating pipe 21 and the penetrating part of the reaction cylinder 1 are sealed mechanically, the bottom end of the rotating pipe 21 is provided with a rotary driving part 3, after air flow enters the rotating pipe 21, the air flow is discharged through a connecting pipe 31, a rotary connector 32 and an exhaust pipe 33 in the rotary driving part 3 and can be discharged to the installation position of a fan for recycling, wherein the exhaust pipe 33 does not need to rotate when the rotating pipe 21 rotates due to the arrangement of the rotary connector 32, and the exhaust pipe 33 preferably uses a hose;
the bottom of the reaction cylinder 1 is provided with a driving part 4 for driving the rotating pipe 21 to rotate, wherein the connecting pipe 31 is provided with a driven gear 34 which is meshed with a driving gear 43 in the driving part 4, when the reaction cylinder works, the motor 42 drives the rotating shaft to rotate so as to drive the driving gear 43 to rotate, the driving gear 43 drives the driven gear 34 to rotate so as to drive the stirring part 2 to rotate for stirring operation, and the top end of the rotating shaft is rotatably connected with the top of the mounting frame 41;
the bottom of the reaction barrel 1 is connected with an annular discharging pipe 6 for discharging, the annular discharging pipe 6 is used for discharging products, the annular discharging pipe 6 is located on the outer sides of the driving piece 4 and the rotary driving piece 3, threads are arranged on the outer side and the inner side surface of the annular discharging pipe 6, a sealing cover 7 is in threaded connection with the annular discharging pipe 6, corresponding threads are arranged on two sides of the inner surface of the sealing cover 7, and the annular discharging pipe and the rotary driving piece are in threaded connection, so that the operation is simple and convenient;
the sealing plug 72 is arranged in the sealing cover 7 and plugged in the annular discharging pipe 6, so that the sealing performance is improved, and the handles are arranged on two sides of the bottom of the sealing cover 7, so that the sealing cover 7 can be conveniently screwed;
the top of the reaction cylinder 1 is provided with a feed pipe, and the feed pipe is in threaded connection with a sealing cover.
The top of the inner wall of the reaction cylinder 1 is provided with a conical guide cover 8, during discharging, reactants can be guided to the interior of the annular discharging pipe, discharging is facilitated, and the guide cover 8 is sleeved on the surface of the rotating pipe 21.
The reaction tube 1 is provided with a temperature sensor 9 for detecting temperature.
Compared with the related technology, the preparation method and the device of the high-content acrylic copolymer provided by the invention have the following beneficial effects:
through dividing reaction cylinder 1 into urceolus 101 and inner tube 102, set up air guide cavity 103 between, and the stirring piece 2 in turn pipe 21 with the inside intercommunication of air guide cavity 103, can let in hot gas flow or cold air current to the inside of air guide cavity 103 and rotation pipe 21 and enter into inside stirring leaf 22 through temperature regulation pipe fitting 5, thereby can heat or cool off the reactant through the inner wall of pivoted stirring leaf and reaction cylinder 1, very big improvement is to the heating or the refrigerated speed of reactant, can cool off the crystallization operation to the reactant.
Twelfth embodiment
Referring to fig. 6 and 7 in combination, a second embodiment of the present application provides another apparatus for preparing a high acrylic copolymer, based on the apparatus for preparing a high acrylic copolymer provided in the eleventh embodiment of the present application.
Specifically, the preparation apparatus for high content acrylic acid copolymer provided in the second embodiment of the present application is different in that, the preparation apparatus for high content acrylic acid copolymer, the rotating pipe 21 includes an upper end pipe 211 and a lower end pipe 212, the upper end pipe 211 and the lower end pipe 212 are connected through a telescopic pipe 13, the telescopic pipe 13 is a plastic pipe capable of stretching, concave folding cross-sections and convex folding cross-sections are alternately arranged on the surface of the plastic pipe, wherein the stirring blade 22 is arranged on the upper end pipe 211, and a telescopic rod 14 is connected between the upper end pipe 211 and the lower end pipe 212, the telescopic rod 14 is preferably provided in two numbers, wherein the telescopic rod 14 includes an outer pipe, a rectangular cavity with a rectangular cross-section is arranged inside the outer pipe, and an inner rod with a rectangular cross-section is arranged inside the rectangular cavity;
the top of upper end pipe 211 sets up for sealing, and the top of upper end pipe 211 runs through reaction cylinder 1 and extends to the outside of reaction cylinder 1, and a plurality of inlet ports 11 have been seted up to the inside annular that upper end pipe 211 is located air guide cavity 103, and the top fixedly connected with of upper end pipe 211 drives board 12, the top fixedly connected with guide 15 of reaction cylinder 1, wherein guide 15 is the annular piece, and the middle height at the bottom of both sides, and the top of 1 urceolus 101 of reaction cylinder is provided with the bellying, and the cavity height of bellying is greater than the highest point height of guide 15.
When driving piece 4 drives rotatory take 3 to rotate, rotatory take 3 to drive lower extreme pipe 212 and rotate, lower extreme pipe 212 passes through telescopic link 14 and drives upper end pipe 211 and rotate, upper end pipe 211 drives stirring leaf 22 initiative, it drives the rotation of drive board 12 simultaneously, when driving board 12 pivoted, along the low side of guide 15 to the high-end removal and remove to the bottom again, thereby can drive upper end pipe 211 reciprocating motion from top to bottom, upper end pipe 211 drives stirring leaf pivoted simultaneously can drive stirring leaf 22 and reciprocate promptly, thereby can increase the area of contact of stirring leaf 22 and reaction liquid, improve the mixing rate of reactant, and heating or refrigerated efficiency.
The above description is only an embodiment of the present invention, and not intended to limit the scope of the present invention, and all modifications of equivalent structures and equivalent processes, which are made by using the contents of the present specification and the accompanying drawings, or directly or indirectly applied to other related technical fields, are included in the scope of the present invention.
Claims (10)
1. A method for preparing a high-content acrylic copolymer is characterized by comprising the following steps:
s1: putting a mixed solution of an acrylic monomer and an unsaturated monomer containing sulfonic acid in a molar ratio of 1: 1-10: 1 into a reaction kettle, adding sodium bisulfite according to 1-15% of the mass of a monomer raw material, heating to 60-95 ℃, then dropwise adding an initiator of 2-15% of the total mass of the monomer raw material, and carrying out polymerization reaction for 6-8 hours to obtain a light yellow to amber transparent liquid;
s2: concentrating the product obtained from the S1 at the temperature of 80-100 ℃ for 6-12 h to obtain a yellowish to amber viscous liquid, wherein the solid content is controlled at 60-80%;
s3: adding solvent absolute ethyl alcohol into the product obtained in the step S2, cooling to 40-60 ℃, and continuously stirring for 2-3 hours;
s4: and (5) adding crystal nucleus sodium acetate into the product obtained in the step S3, cooling, crystallizing, centrifugally dewatering and drying to obtain the final product.
2. The method of claim 1, wherein the sulfonic acid-containing unsaturated monomer in S1 is 2-acrylamido-2-methylpropanesulfonic acid and salts thereof or allylsulfonic acid and salts thereof.
3. The method for preparing the high-content acrylic copolymer as claimed in claim 1, wherein the initiator in the S1 is sodium persulfate, ammonium persulfate or hydrogen peroxide.
4. An apparatus for producing a high acrylic copolymer, which is used in the method for producing a high acrylic copolymer according to any one of claims 1 to 3, comprising:
the reaction cylinder (1), the reaction cylinder (1) includes an outer cylinder (101) and an inner cylinder (102), the inner cylinder (102) is fixed in the outer cylinder (101), and a gas conducting cavity is formed between the outer cylinder (101) and the inner cylinder (102);
the stirring part (2) comprises a rotating pipe (21), the top end of the rotating pipe (21) penetrates through the inner cylinder (102) and extends to the inside of the air guide cavity, the top end of the rotating pipe (21) is communicated with the inside of the air guide cavity, a stirring blade (22) is fixedly connected to the surface of the rotating pipe (21) and located inside the reaction cylinder 1, and the inside of the stirring blade (22) is communicated with the inside of the rotating pipe (21);
the rotary driving piece (3), the rotary driving piece (3) is connected to the bottom end of the rotating pipe (21) and is positioned outside the reaction cylinder (1);
the driving piece (4) is fixedly arranged at the bottom of the reaction cylinder (1), and the driving piece (4) is in transmission connection with the rotary driving piece 3;
the temperature adjusting pipe fitting (5), the temperature adjusting pipe fitting (5) connect in the installation pipe (10) of reaction cylinder (1) one side.
5. The method and the device for preparing the high content acrylic acid copolymer according to claim 4, wherein the temperature adjusting pipe (5) comprises a tee pipe (51), L-shaped pipes (52) are connected to both ends of the tee pipe (51), one ends of the two L-shaped pipes (52) are respectively connected with a cooling pipe 53 and a hot air pipe (54), and valves (55) are mounted on the two L-shaped pipes (52).
6. The method and apparatus for preparing high content acrylic copolymer according to claim 4, wherein the rotary driving member (3) comprises a connecting pipe (31), the connecting pipe (31) is connected to the bottom end of the rotating pipe (2), the bottom end of the connecting pipe (31) is connected to a rotary connector (32), and one end of the rotary connector (32) is connected to an exhaust pipe (33).
7. The method and the device for preparing the high content acrylic copolymer according to claim 6, wherein the driving member (4) comprises a mounting frame (41), the mounting frame (41) is fixed at the bottom of the reaction cylinder (1), a motor (42) is fixedly installed at the bottom of the mounting frame (41), one end of an output shaft of the motor (42) is fixedly connected with a rotating shaft through a coupler, and a driving gear (43) is fixedly connected to the surface of the rotating shaft.
8. The method and apparatus for preparing high acrylic copolymer according to claim 7, wherein the driving gear (43) is engaged with the driven gear (34).
9. The method and apparatus for preparing high content acrylic acid copolymer according to claim 4, wherein the bottom of the reaction cylinder 1 is connected with an annular discharging pipe 6, the annular discharging pipe 6 is connected with a sealing cover (7) in a threaded manner, the sealing cover (7) comprises an annular cover (71), and a sealing plug (72) is installed inside the annular cover (71).
10. The method and apparatus for preparing high acrylic copolymer according to claim 4, wherein the top of the reaction cylinder (1) is provided with a feeding tube, and the reaction cylinder (1) is provided with a temperature sensor (9).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111129203.7A CN113817092A (en) | 2021-09-26 | 2021-09-26 | Preparation method and device of high-content acrylic copolymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111129203.7A CN113817092A (en) | 2021-09-26 | 2021-09-26 | Preparation method and device of high-content acrylic copolymer |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN113817092A true CN113817092A (en) | 2021-12-21 |
Family
ID=78921181
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111129203.7A Pending CN113817092A (en) | 2021-09-26 | 2021-09-26 | Preparation method and device of high-content acrylic copolymer |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113817092A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117329776A (en) * | 2023-09-27 | 2024-01-02 | 葫芦岛市铭浩新能源材料有限公司 | Cooling equipment for coating negative electrode material |
-
2021
- 2021-09-26 CN CN202111129203.7A patent/CN113817092A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117329776A (en) * | 2023-09-27 | 2024-01-02 | 葫芦岛市铭浩新能源材料有限公司 | Cooling equipment for coating negative electrode material |
| CN117329776B (en) * | 2023-09-27 | 2024-03-22 | 葫芦岛市铭浩新能源材料有限公司 | Cooling equipment for coating negative electrode material |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109200984B (en) | Reation kettle with dual heat dissipation function | |
| CN113817092A (en) | Preparation method and device of high-content acrylic copolymer | |
| CN212818229U (en) | Crystallizer with stirring function | |
| CN215028787U (en) | Stirring reaction kettle with composite stirrer | |
| CN205413010U (en) | Adjustable reation kettle of portable stirring radius | |
| CN213078141U (en) | Novel production facility of high content 2-chloroethanol | |
| CN208553201U (en) | A kind of crystallizer for ion-exchange-resin process synthesis of bisphenol A | |
| CN208465853U (en) | A kind of acrylic emulsion without paddle reaction unit | |
| CN116650986A (en) | Distillation type chemical industry reation kettle | |
| CN210419269U (en) | System for preparing long-crystal-grade primary boron oxide | |
| CN211070054U (en) | Large-volume ternary cathode material precursor reaction kettle | |
| CN210545090U (en) | Large-volume ternary anode material precursor reaction kettle with high heat transfer efficiency | |
| CN110193332B (en) | Large-volume ternary anode material precursor reaction kettle | |
| CN219400144U (en) | Mixed reaction kettle for producing water treatment scale inhibitor | |
| CN220552123U (en) | Coating processing cooling device | |
| CN217465446U (en) | Novel heat exchanger | |
| CN220758048U (en) | Continuous cooling crystallization apparatus for producing | |
| CN221905837U (en) | Cooling reflux device of waste mineral oil distillation tower | |
| CN214716613U (en) | Preparation device of ternary cathode material precursor | |
| CN219209940U (en) | Intelligent temperature control type mixing reaction kettle | |
| CN211910480U (en) | Temperature detection system of pellet feed production cooler | |
| CN211798913U (en) | Citric acid concentration and evaporation system | |
| CN212309582U (en) | Chemical reaction kettle | |
| CN214289039U (en) | Expanded polytetrafluoroethylene film surface treatment device | |
| CN219051298U (en) | Automatic temperature control device of reaction kettle |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |