CN116396447A - Preparation method and application of polymer cement grinding aid - Google Patents
Preparation method and application of polymer cement grinding aid Download PDFInfo
- Publication number
- CN116396447A CN116396447A CN202310177808.6A CN202310177808A CN116396447A CN 116396447 A CN116396447 A CN 116396447A CN 202310177808 A CN202310177808 A CN 202310177808A CN 116396447 A CN116396447 A CN 116396447A
- Authority
- CN
- China
- Prior art keywords
- grinding aid
- cement grinding
- cement
- lignin sulfonate
- heating
- 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.)
- Granted
Links
- 238000000227 grinding Methods 0.000 title claims abstract description 54
- 239000011414 polymer cement Substances 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000004568 cement Substances 0.000 claims abstract description 57
- YDEXUEFDPVHGHE-GGMCWBHBSA-L disodium;(2r)-3-(2-hydroxy-3-methoxyphenyl)-2-[2-methoxy-4-(3-sulfonatopropyl)phenoxy]propane-1-sulfonate Chemical group [Na+].[Na+].COC1=CC=CC(C[C@H](CS([O-])(=O)=O)OC=2C(=CC(CCCS([O-])(=O)=O)=CC=2)OC)=C1O YDEXUEFDPVHGHE-GGMCWBHBSA-L 0.000 claims abstract description 32
- -1 polydimethylsiloxane Polymers 0.000 claims abstract description 30
- 239000000178 monomer Substances 0.000 claims abstract description 20
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 13
- 239000004205 dimethyl polysiloxane Substances 0.000 claims abstract description 13
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims abstract description 13
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 13
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 12
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 12
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims abstract description 11
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-UHFFFAOYSA-N 0.000 claims abstract description 10
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims abstract description 10
- SONHXMAHPHADTF-UHFFFAOYSA-M sodium;2-methylprop-2-enoate Chemical compound [Na+].CC(=C)C([O-])=O SONHXMAHPHADTF-UHFFFAOYSA-M 0.000 claims abstract 2
- 238000010438 heat treatment Methods 0.000 claims description 29
- 238000000034 method Methods 0.000 claims description 29
- 238000003756 stirring Methods 0.000 claims description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 18
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 239000011259 mixed solution Substances 0.000 claims description 15
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 14
- 238000001816 cooling Methods 0.000 claims description 14
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 12
- 239000003054 catalyst Substances 0.000 claims description 11
- 239000008367 deionised water Substances 0.000 claims description 11
- 229910021641 deionized water Inorganic materials 0.000 claims description 11
- 239000003112 inhibitor Substances 0.000 claims description 11
- 238000006116 polymerization reaction Methods 0.000 claims description 11
- 238000010992 reflux Methods 0.000 claims description 11
- 239000008098 formaldehyde solution Substances 0.000 claims description 9
- 229910052710 silicon Inorganic materials 0.000 claims description 9
- 239000010703 silicon Substances 0.000 claims description 9
- SZHIIIPPJJXYRY-UHFFFAOYSA-M sodium;2-methylprop-2-ene-1-sulfonate Chemical compound [Na+].CC(=C)CS([O-])(=O)=O SZHIIIPPJJXYRY-UHFFFAOYSA-M 0.000 claims description 9
- 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 8
- 238000004090 dissolution Methods 0.000 claims description 8
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 8
- 229960000583 acetic acid Drugs 0.000 claims description 7
- 239000012362 glacial acetic acid Substances 0.000 claims description 7
- 230000007935 neutral effect Effects 0.000 claims description 6
- 229920005552 sodium lignosulfonate Polymers 0.000 claims description 6
- 238000007599 discharging Methods 0.000 claims description 5
- 230000001105 regulatory effect Effects 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 4
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 4
- 239000004593 Epoxy Substances 0.000 claims description 2
- 238000004321 preservation Methods 0.000 claims description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims 1
- 239000002245 particle Substances 0.000 abstract description 15
- 230000000694 effects Effects 0.000 abstract description 14
- 238000004519 manufacturing process Methods 0.000 abstract description 10
- 239000004721 Polyphenylene oxide Substances 0.000 abstract description 6
- 229920000570 polyether Polymers 0.000 abstract description 6
- 125000000524 functional group Chemical group 0.000 abstract description 5
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 abstract description 4
- 229910018557 Si O Inorganic materials 0.000 abstract description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 3
- 238000007334 copolymerization reaction Methods 0.000 abstract description 2
- 238000005886 esterification reaction Methods 0.000 abstract description 2
- 230000035876 healing Effects 0.000 abstract description 2
- 239000006185 dispersion Substances 0.000 abstract 1
- 239000000463 material Substances 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 238000012360 testing method Methods 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- 238000001035 drying Methods 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 239000011083 cement mortar Substances 0.000 description 5
- 238000005265 energy consumption Methods 0.000 description 5
- 230000001276 controlling effect Effects 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 239000003999 initiator Substances 0.000 description 3
- 229920005610 lignin Polymers 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000003825 pressing Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 150000003385 sodium Chemical class 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 241000218378 Magnolia Species 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000011010 flushing procedure Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000004570 mortar (masonry) Substances 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 206010003591 Ataxia Diseases 0.000 description 1
- 235000019738 Limestone Nutrition 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000010881 fly ash Substances 0.000 description 1
- 239000013505 freshwater Substances 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 239000006028 limestone Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000010079 rubber tapping Methods 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 238000005029 sieve analysis Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
- 238000005303 weighing Methods 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
- C08F285/00—Macromolecular compounds obtained by polymerising monomers on to preformed graft polymers
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/16—Sulfur-containing compounds
- C04B24/18—Lignin sulfonic acid or derivatives thereof, e.g. sulfite lye
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B7/00—Hydraulic cements
- C04B7/36—Manufacture of hydraulic cements in general
- C04B7/48—Clinker treatment
- C04B7/52—Grinding ; After-treatment of ground cement
-
- 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
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
- C08F283/065—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals on to unsaturated polyethers, polyoxymethylenes or polyacetals
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/52—Grinding aids; Additives added during grinding
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P40/00—Technologies relating to the processing of minerals
- Y02P40/10—Production of cement, e.g. improving or optimising the production methods; Cement grinding
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
The invention discloses a preparation method and application of a polymer cement grinding aid. According to the invention, diethanolamine is grafted into a sodium lignin sulfonate structure, and then reacts with allyl glycidyl ether and epoxy-terminated polydimethylsiloxane to obtain a product; esterification reaction is carried out on acrylic acid and polyethylene glycol to obtain an esterified monomer; and (3) carrying out copolymerization reaction on the product, sodium methacrylate, maleic anhydride and esterified monomer to obtain the high-molecular cement grinding aid. The long polyether side chain can provide a large steric hindrance effect, so that the dispersion performance of the particles is improved; the short chain contains Si-O bond, hydroxyl and other functional groups, is easy to adsorb on material particles, has negative charge, plays an electrostatic repulsive action between cement particles, and prevents crack interfaces from healing again. The product of the invention has obvious grinding assisting effect, improves grinding efficiency, reduces power consumption and production cost of the product, and improves cement performance.
Description
Technical Field
The invention relates to the technical field of cement production, in particular to a preparation method and application of a polymer cement grinding aid.
Background
In the cement production process, the energy consumption of the grinding process is high, and the energy consumption of cement production is high, so that the cement grinding aid has become one of effective measures for improving the grinding efficiency, reducing the grinding power consumption, improving the cement performance and reducing the production cost.
The polymer cement grinding aid plays roles of surface activity, dispersibility and functional groups thereof in the cement production process to realize the grinding aid effect, wherein a polycarboxylic acid cement grinding aid can be obtained by copolymerizing an unsaturated monomer and other monomers under the action of an initiator, and the polycarboxylic acid cement grinding aid is a polymer with the grinding aid effect, which is obtained by grafting a side chain with active groups onto a main chain. Different unsaturated monomers, different active monomers containing functional groups and different combination modes among the monomers, and different synthetic technical routes, so that a plurality of polycarboxylic acid copolymers with different structures and performance characteristics can be obtained. Although the traditional grinding aid has good grinding aid effect, the traditional grinding aid has poor compatibility with cement, and air holes can be formed in the cement in the pouring process, so that the quality of the cement is affected. Accordingly, intensive research into cement grinding aids is required.
Disclosure of Invention
The invention aims to provide a preparation method and application of a polymer cement grinding aid, so as to solve the problems in the background technology.
In order to solve the technical problems, the invention provides the following technical scheme:
the preparation method of the high polymer cement grinding aid comprises the following steps:
(1) Adding sodium lignin sulfonate into deionized water, uniformly mixing, and then adding diethanolamine; ultrasonic dispersing for 15-25 min, heating to 70-80 ℃, slowly dripping formaldehyde solution, and carrying out constant-temperature reflux reaction for 2-4 h to obtain modified sodium lignin sulfonate;
(2) Adding modified sodium lignin sulfonate and glacial acetic acid into allyl glycidyl ether, stirring thoroughly, heating to 50 ℃, adding epoxy end-capped polydimethylsiloxane, heating to 70-80 ℃ continuously, reacting for 4-5 hours at a constant temperature, distilling for 3-5 hours under reduced pressure, cooling, and discharging to obtain the organosilicon modified sodium lignin sulfonate;
(3) Mixing the esterified macromonomer with maleic anhydride to prepare monomer mixed solution; adding sodium methallyl sulfonate into deionized water, and stirring for dissolution; heating to 75-85 ℃, and dropwise adding the monomer mixed solution and the sodium persulfate initiator aqueous solution for 4-6 hours; then adding organic silicon modified sodium lignosulfonate, and reacting for 2-3 h under heat preservation; and (3) cooling to room temperature, and regulating the pH value to be neutral to obtain the high-molecular cement grinding aid.
Further, the esterified macromer is prepared by the following process:
taking polyethylene glycol, adding a polymerization inhibitor hydroquinone and a catalyst p-toluenesulfonic acid, heating to 70-80 ℃ for dissolution, adding acrylic acid, stirring and heating to 110-120 ℃, and reacting for 8-10 h to obtain the esterified macromonomer.
Further, the epoxy-terminated polydimethylsiloxane is glycidoxypropyl-terminated polydimethylsiloxane, which is purchased from Shanghai Michelia Biochemical technology Co., ltd, and has a purity of not less than 98% and a mass average molecular weight MW of 2000-3000;
further, the mass ratio of the sodium lignin sulfonate to the deionized water in the step (1) is (1:1) - (1:4).
Further, the mass ratio of the diethanolamine to the sodium lignin sulfonate in the step (1) is (1:1) - (1:1.5).
Further, the formaldehyde solution in the step (1) has the mass fraction of 37% and the dosage of 1.25-5.30 times of that of sodium lignin sulfonate.
Further, the mass ratio of the allyl glycidyl ether to the glycidoxypropyl end-capped polydimethylsiloxane in the step (2) is (1:1) - (2:1).
Further, the glacial acetic acid dosage in the step (2) is 0.54 to 0.85 times of the mass of the glycidoxypropyl terminated polydimethylsiloxane.
Further, the dosage of the hydroquinone and the p-toluenesulfonic acid is 0.02-0.05 times of the mass of the polyethylene glycol.
Further, the mass ratio of the polyethylene glycol to the acrylic acid is (1:10) - (1:14).
Further, the mass ratio of the sodium methallyl sulfonate to the acrylic acid in the step (3) is (1:1) - (1:2).
Further, the sodium persulfate in the step (3) accounts for 3.3 to 4.2 percent of the total mass of the reaction monomers (the total mass of the esterified macromer and the maleic anhydride).
Compared with the prior art, the invention has the following beneficial effects:
(1) The invention prepares the organosilicon modified sodium lignin sulfonate by reacting sodium lignin sulfonate containing a large amount of functional groups such as phenolic hydroxyl groups, methoxy groups, benzyl hydroxyl groups and the like with formaldehyde and diethanolamine, and then reacting the sodium lignin sulfonate with allyl glycidyl ether and glycidoxypropyl terminated polydimethylsiloxane; acrylic acid and polyethylene glycol are subjected to esterification reaction under the conditions of a catalyst and a polymerization inhibitor; the organic silicon modified sodium lignin sulfonate is used as a synthetic material, and is subjected to graft copolymerization reaction with sodium methallyl sulfonate, maleic anhydride and the obtained esterified macromonomer under the action of an initiator to obtain a final product, namely the high molecular cement grinding aid. Because the polyether has longer polyether side chains and contains various functional groups such as Si-O bonds, hydroxyl groups and the like, the polyether side chains can be easily adsorbed on the surfaces of cement particles, negative charges in molecules can lead the particles to generate static electricity so as to generate repulsive phenomenon, the effects of dispersing the particles and preventing healing of crack interfaces are achieved, in addition, the Si-O bonds have extremely high surface activity and dispersibility, the free energy of the surfaces of the cement particles can be effectively reduced, the longer polyether side chains can exert larger steric hindrance effect, the dispersing effect of the cement particles is further enhanced, the effect of accelerating crack expansion is achieved, and the energy generated in the cement production process can be more crushed by dry cement particles so that the particles are more uniform and fine, thereby achieving the aims of improving the cement grinding efficiency and reducing the cement energy consumption.
(2) The electrostatic repulsion effect generated by negative charge of the organosilicon modified sodium lignin sulfonate can be combined with the steric hindrance effect of a long polyether side chain, so that the surface tension can be reduced, the lubrication among cement particles can be promoted, water can fully enter into micro gaps among the cement particles, the fluidity of cement is improved, the grinding process in the cement production process is improved, the energy consumption is reduced, the production efficiency is improved, and the production cost is reduced.
Detailed Description
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
In this example, sodium lignin sulfonate was purchased from Tianjin Hien Biochemical Co., ltd; diethanolamine was purchased from Shanghai Ala Biochemical technologies Co., ltd., analytical grade; the mass fraction of the formaldehyde solution is 37%, and the formaldehyde solution is purchased from Beijing Happy biotechnology Co., ltd; allyl glycidyl ether was purchased from Shanghai Kappa chemical Co., ltd; the glycidoxypropyl end-capped polydimethylsiloxane is purchased from Shanghai Michelia Biochemical technology Co., ltd, the purity is more than or equal to 98%, and the mass average molecular weight MW is 2000-3000; glacial acetic acid was purchased from shandong rui double chemical engineering limited; polyethylene glycol was purchased from Shanghai Seiyaka Biotechnology Co., ltd and has a molecular weight of 1000; hydroquinone was purchased from south Beijing blue albino company, inc.; p-toluenesulfonic acid was purchased from Shanghai Yi En chemical technologies Co., ltd; sodium methallyl sulfonate was purchased from Shanghai Siemens Biotechnology Co.Ltd; maleic anhydride was purchased from Shandong Xu Chemie technology Co., ltd; sodium persulfate was purchased from ataxia century to chemical industry limited; the sodium hydroxide solution was 30% by mass and was purchased from Shanghai Bohr chemical Co.
Example 1: the preparation method of the high polymer cement grinding aid comprises the following steps:
(1) Adding 50g of sodium lignin sulfonate and 100ml of deionized water into a three-neck flask with stirring reflux, stirring at 300r/min for 10min, adding 60g of diethanolamine, performing ultrasonic dispersion for 15min, heating to 70 ℃, dropwise adding 150g of 37% formaldehyde solution at 2g/min, and performing constant-temperature reflux reaction for 2h; cooling to room temperature, rotary distilling for 3h to remove solvent water, adding 250ml of absolute ethyl alcohol, standing for 20min, suction filtering to obtain filter residue, and drying in a 45 ℃ drying oven for 6h to obtain modified lignin sodium sulfate;
(2) Taking 75g of allyl glycidyl ether to a flask, adding 100g of modified sodium lignin sulfonate and 45g of glacial acetic acid, stirring for 10min at 300r/min, starting heating, adding 60g of glycidoxypropyl terminated polydimethylsiloxane when the temperature is 50 ℃, continuously heating to 70 ℃, and carrying out constant-temperature reflux reaction for 4h; after the reaction is finished, carrying out reduced pressure distillation for 3 hours, cooling and discharging to obtain the organic silicon modified sodium lignin sulfonate;
(3) Adding 300g of polyethylene glycol, 2g of polymerization inhibitor hydroquinone and 2g of catalyst p-toluenesulfonic acid into a three-neck flask with a stirring and condensing device respectively, heating to 70 ℃ for dissolution, adding 30g of acrylic acid, stirring and heating to 110 ℃, and finishing the reaction for 8 hours; separating out the catalyst and the polymerization inhibitor in colorless crystals, and separating to obtain an esterified macromonomer;
(4) Adding 250ml of deionized water into a four-neck flask provided with a stirring device and a condensing device, adding 40g of sodium methallyl sulfonate, stirring and dissolving, simultaneously taking 30g of esterified macromer and 90g of maleic anhydride to prepare a monomer mixed solution, heating to 75 ℃, dropwise adding the monomer mixed solution, and controlling the dropwise adding time to be 4 hours; adding 6g of sodium persulfate, adding 70g of organic silicon modified sodium lignosulfonate into the mixed solution, preserving heat for 2 hours, cooling to room temperature, and regulating the pH value to be neutral by using 30% sodium hydroxide solution to obtain the high polymer cement grinding aid.
Example 2: the preparation method of the high polymer cement grinding aid comprises the following steps:
(1) Adding 75g of sodium lignin sulfonate and 150ml of deionized water into a three-neck flask with stirring reflux, stirring for 15min at 350r/min, adding 90g of diethanolamine, performing ultrasonic dispersion for 20min, heating to 75 ℃, dropwise adding 200g of 37% formaldehyde solution at 3g/min, and performing constant-temperature reflux reaction for 3h; cooling to room temperature, rotary distilling for 4 hr to remove solvent water, adding 350ml of absolute ethyl alcohol, standing for 25min, vacuum filtering to obtain residue, and drying in a 45 deg.C drying oven for 7 hr to obtain modified lignin sodium sulfate;
(2) Taking 80g of allyl glycidyl ether to a flask, adding 110g of modified sodium lignin sulfonate and 50g of glacial acetic acid, stirring for 15min at 350r/min, starting heating, adding 65g of glycidoxypropyl terminated polydimethylsiloxane when the temperature is 50 ℃, continuously heating to 75 ℃, and carrying out constant-temperature reflux reaction for 4.5h; after the reaction is finished, carrying out reduced pressure distillation for 4 hours, cooling and discharging to obtain the organic silicon modified sodium lignin sulfonate;
(3) 400g of polyethylene glycol, 3g of polymerization inhibitor hydroquinone and 3g of catalyst p-toluenesulfonic acid are respectively added into a three-neck flask with a stirring and condensing device; after heating to 75 ℃ for dissolution, 40g of acrylic acid is added, stirred and heated to 115 ℃, and the reaction is finished for 9 hours; separating out the catalyst and the polymerization inhibitor in colorless crystals, and separating to obtain an esterified macromonomer;
(4) Adding 300ml of deionized water into a four-neck flask provided with a stirring device and a condensing device, adding 50g of sodium methallyl sulfonate, stirring and dissolving, simultaneously taking 40g of esterified macromer and 120g of maleic anhydride to prepare a monomer mixed solution, heating to 80 ℃, dropwise adding the monomer mixed solution, and controlling the dropwise adding time to be 5 hours; adding 8g of sodium persulfate, adding 110g of organic silicon modified sodium lignosulfonate into the mixed solution, preserving heat for 2.5h, cooling to room temperature, and regulating the pH value to be neutral by using 30% sodium hydroxide solution to obtain the modified sodium lignosulfonate grafted polycarboxylic acid cement grinding aid.
Example 3: the preparation method of the high polymer cement grinding aid comprises the following steps:
(1) Adding 100g of sodium lignin sulfonate and 200ml of deionized water into a three-neck flask with stirring reflux, stirring for 20min at 450r/min, adding 120g of diethanolamine, performing ultrasonic dispersion for 25min, heating to 80 ℃, dropwise adding 250g of 37% formaldehyde solution at 4g/min, and performing constant-temperature reflux reaction for 4h; rotary distillation is carried out for 5 hours after proper cooling for removing solvent water, then 400ml of absolute ethyl alcohol is added, after standing for 30 minutes, filter residues are obtained through suction filtration, and the filter residues are put into a drying oven at 45 ℃ for drying for 8 hours, thus obtaining modified sodium lignin sulfate;
(2) 85g of allyl glycidyl ether is taken to a flask, 120g of modified sodium lignin sulfonate and 55g of glacial acetic acid are added, stirring is carried out for 20min at 400r/min, heating is started, 70g of glycidoxypropyl terminated polydimethylsiloxane is added when the temperature is 50 ℃, the temperature is continuously raised to 80 ℃, and the constant-temperature reflux reaction is carried out for 5h; vacuum distillation is carried out for 5 hours after the reaction is finished, and cooling and discharging are carried out to obtain the organic silicon modified sodium lignin sulfonate;
(3) 500g of polyethylene glycol, 4g of polymerization inhibitor hydroquinone and 4g of catalyst p-toluenesulfonic acid are respectively added into a three-neck flask provided with a stirring and condensing device; after heating to 80 ℃ for dissolution, 50g of acrylic acid is added, stirred and heated to 120 ℃, and the reaction is finished for 10 hours; separating out the catalyst and the polymerization inhibitor in colorless crystals, and separating to obtain an esterified macromonomer;
(4) Adding 350ml of deionized water into a four-neck flask provided with a stirring device and a condensing device, adding 60g of sodium methallyl sulfonate, stirring and dissolving, simultaneously taking 50g of esterified macromer and 150g of maleic anhydride to prepare a monomer mixed solution, heating to 85 ℃, dropwise adding the monomer mixed solution, and controlling the dropwise adding time to be 5 hours; adding 10g of sodium persulfate, adding 150g of organic silicon modified sodium lignin sulfonate into the mixed solution, preserving heat for 3 hours, cooling to room temperature, and regulating the pH value to be neutral by using 30% sodium hydroxide solution to obtain the modified sodium lignosulfonate grafted polycarboxylic acid cement grinding aid.
Comparative example 1: a preparation method of a macromolecular cement grinding aid,
compared with example 2, comparative example 1 was free of sodium lignin sulfonate, and 60g of polyethylene glycol, 2g of hydroquinone as a polymerization inhibitor and 2g of p-toluenesulfonic acid as a catalyst were added to a three-necked flask equipped with a stirring and condensing device, respectively; after heating to 70 ℃ for dissolution, 60g of acrylic acid is added, stirred and heated to 110 ℃, and the reaction is finished for 6 hours; separating out the catalyst and the polymerization inhibitor in colorless crystals, and separating to obtain an esterified macromonomer; adding 50g of sodium methallyl sulfonate, stirring and dissolving, simultaneously taking 40g of esterified macromer and 120g of maleic anhydride to prepare a monomer mixed solution, heating to 80 ℃, dropwise adding the monomer mixed solution, and controlling the dropwise adding time to be 5 hours; 8g of sodium persulfate is added, then the temperature is kept for 2.5 hours, and after cooling to room temperature, the pH is adjusted to be neutral by 30% sodium hydroxide solution, thus obtaining the polymer cement grinding aid.
Comparative example 2: a preparation method of a macromolecular cement grinding aid,
compared to example 2, comparative example 2 deleted step (1-2) and replaced the silicone modified sodium lignin sulfonate in step (4) with equal mass sodium lignin sulfonate; the other steps were the same as in example 2 to obtain a polymer cement grinding aid.
Comparative example 3: a preparation method of a macromolecular cement grinding aid,
compared with example 2, comparative example 3 was carried out by deleting step (2), replacing the organosilicon modified sodium lignin sulfonate in step (4) with the modified sodium lignin sulfonate in equal mass step (1), and obtaining the polymer cement grinding aid in step (3-4) as in example 2.
Experiment
Taking the cement grinding aids obtained in examples 1-3 and comparative examples 1-3, preparing samples, respectively detecting the performances of the samples and recording the detection results:
cement proportion (mass fraction, the following are the same): 70% of clinker, 5% of gypsum, 6% of limestone, 9% of fly ash and 10% of slag: phi 500mmx500mm ball mill, grinding aid dosage is 0.05%, grinding for 36min.
According to the water sieve method in GB 1345-2005 (80 μm sieve analysis method) for testing the fineness of cement, the experimental steps are as follows: before a screen analysis test, the water should be checked for mud and sand, the water pressure and the position of the water screen frame should be adjusted so that the water screen frame can normally run, and the distance between the bottom surface of the spray head and the screen is controlled to be 35 mm-75 mm. Weighing the sample to 0.01g, placing the sample in a clean water sieve, immediately flushing most of the fine powder by fresh water until the fine powder passes through the sieve, placing the sample on a water sieve frame, and continuously flushing the sample for 3min by a spray head with the water pressure of 0.05MPa plus or minus 0.02 MPa. After sieving, the residue is washed into an evaporating dish with a small amount of water, after all cement particles are precipitated, the clean water is carefully poured out, and the residue is dried and weighed by a balance.
According to GB/T17671-2021 method for testing cement mortar strength (ISO method), the flexural strength of cement mortar is measured, and the experimental steps are as follows: the mortar meeting the consistency requirement is made into a 40mmx40mmx160mm prism test body, and the prism test body is placed in a standard curing box with constant temperature of 25 ℃ and relative humidity of 95 percent, and is respectively cured for 3d and 28d for measurement.
According to GB/T17671-2021 method for testing cement mortar strength (ISO method), the compressive strength of cement mortar is measured, and the experimental steps are as follows: and (3) preparing the mortar meeting the consistency requirement into a module by adopting a 40mmx40mmx160mm prismatic test body model, placing the module in a standard curing box with constant temperature of 25 ℃ and relative humidity of 95%, curing for 3d and 28d respectively, and measuring the compressive strength of the cement mortar. In the test process, the difference between the center of the half prism and the compression center of the pressing plate of the pressing machine is within +/-0.5 mm, the part of the prism exposed outside the pressing plate is about 10mm, and the prism is uniformly loaded at the speed of 2400 +/-200N/s until the prism is damaged in the whole loading process.
According to GB/T8074-2008 ' method for measuring specific surface area of Cement (Bo's method) ', the specific surface area of cement is measured, and the experimental steps are as follows: the cement sample is fully and uniformly mixed, passes through a square hole sieve with 0.9mm, is dried at the temperature of 110+/-5 ℃ and is cooled to room temperature in a dryer, is poured into a 100ml closed bottle, is shaken for 2min by force, and is crushed by shaking to loose the agglomerated sample. After standing for 2min, opening a bottle cap, and slightly stirring to ensure that the fine powder falling onto the surface in the loosening process is distributed into the whole sample; the standard sample amount for the calibration test and the mass of the cement to be measured were adjusted to a void fraction of 0.500 to 0.005 in the sample layer prepared, the perforated plate was placed on the flange of the air-permeable cylinder, and a piece of filter paper was fed onto the perforated plate with a thin rod having a diameter slightly smaller than that of the cylinder, and the edges were pressed. The cement was weighed to an accuracy of 0.001g and poured into a cylinder. Tapping the edge of the cylinder to level the surface of the cement layer; putting a piece of filter paper, uniformly tamping the sample by using a tamping machine until a supporting ring of the tamping machine is tightly contacted with the top edge of the cylinder and rotates for two weeks, and slowly taking out the tamping machine; connecting a breathable circle with a test layer to a pressure gauge, wherein the test layer is prepared without air leakage and vibration; the micro electromagnetic pump is turned on to slowly pump air out of one arm of the pressure gauge until the liquid level in the pressure gauge rises to the lower end of the expansion part, and the valve is closed. And starting timing when the liquid level in the pressure gauge is lowered to the first scribing line, stopping timing when the liquid level is lowered to the second scribing line, and recording the time required for the liquid level to reach the second scribing line from the first scribing line. The temperature in seconds was recorded and the temperature at the time of the test was recorded (C.).
From the data in the above table, the following conclusions can be clearly drawn:
1. compared with the examples 1-3, the fineness, the flexural strength, the compressive strength and the specific surface area of the product obtained in the comparative example 1 are all reduced, and the modified sodium lignin sulfonate and the process thereof can improve the performance of the cement grinding aid;
2. the fineness, flexural strength, compressive strength and specific surface area of the products obtained in examples 1-3 were all improved compared to comparative example 1, demonstrating that the incorporation of diethanolamine into sodium lignin sulfonate increases its polar structure and imparts a typical cement grinding aid group.
3. Compared with comparative example 2, the fineness, flexural strength, compressive strength and specific surface area of the product obtained in comparative example 3 are all improved, and Si-0 bond has extremely high surface activity and dispersibility, so that the free energy of the surface of cement particles can be effectively reduced, the particles are more uniform and fine, and the aims of improving the cement grinding efficiency and reducing the cement energy consumption are fulfilled.
It is noted that relational terms such as first and second, and the like are used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Moreover, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process method article or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process method article or apparatus.
Finally, it should be noted that: the foregoing description is only a preferred embodiment of the present invention, and the present invention is not limited thereto, but it is to be understood that modifications and equivalents of some of the technical features described in the foregoing embodiments may be made by those skilled in the art, although the present invention has been described in detail with reference to the foregoing embodiments. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (9)
1. The preparation method of the high polymer cement grinding aid is characterized by comprising the following steps of:
(1) Adding sodium lignin sulfonate into deionized water, uniformly mixing, adding diethanolamine, performing ultrasonic dispersion for 15-25 min, heating to 70-80 ℃, slowly dropwise adding formaldehyde solution, and performing constant-temperature reflux reaction for 2-4 h to obtain modified sodium lignin sulfonate;
(2) Adding modified sodium lignin sulfonate and glacial acetic acid into allyl glycidyl ether, stirring thoroughly, heating to 50 ℃, adding epoxy end-capped polydimethylsiloxane, heating to 70-80 ℃ continuously, reacting for 4-5 hours at a constant temperature, distilling for 3-5 hours under reduced pressure, cooling, and discharging to obtain the organosilicon modified sodium lignin sulfonate;
(3) Mixing an esterified macromonomer with maleic anhydride to prepare a monomer mixed solution; adding sodium methallyl sulfonate into deionized water, and stirring for dissolution; heating to 75-85 ℃, and dripping the monomer mixed solution for 4-6 hours; adding sodium persulfate, adding organic silicon modified sodium lignosulfonate, and reacting for 2-3 h under heat preservation; and (3) cooling to room temperature, and regulating the pH value to be neutral to obtain the high-molecular cement grinding aid.
2. The method for preparing the macromolecular cement grinding aid according to claim 1, which is characterized by comprising the following steps: the esterified macromer is prepared by the following process:
taking polyethylene glycol, adding a polymerization inhibitor hydroquinone and a catalyst p-toluenesulfonic acid, heating to 70-80 ℃ for dissolution, adding acrylic acid, stirring and heating to 110-120 ℃, and reacting for 8-10 h to obtain the esterified macromonomer.
3. The method for preparing the macromolecular cement grinding aid according to claim 1, which is characterized by comprising the following steps: the mass ratio of the diethanolamine to the sodium lignin sulfonate in the step (1) is (1:1) - (1:1.5).
4. The method for preparing the macromolecular cement grinding aid according to claim 1, which is characterized by comprising the following steps: the dosage of the formaldehyde solution used in the step (1) is 1.25 to 5.30 times of that of sodium lignin sulfonate.
5. The method for preparing the macromolecular cement grinding aid according to claim 1, which is characterized by comprising the following steps: and (3) the mass ratio of the allyl glycidyl ether to the epoxy-terminated polydimethylsiloxane in the step (2) is (1:1) - (2:1).
6. The method for preparing the macromolecular cement grinding aid according to claim 2, which is characterized by comprising the following steps: the dosage of the hydroquinone and the p-toluenesulfonic acid is 0.02-0.05 times of the mass of the polyethylene glycol.
7. The method for preparing the macromolecular cement grinding aid according to claim 2, which is characterized by comprising the following steps: the mass ratio of the polyethylene glycol to the acrylic acid is (1:10) - (1:14).
8. The method for preparing the macromolecular cement grinding aid according to claim 2, which is characterized by comprising the following steps: the mass ratio of the sodium methacrylate sulfonate to the acrylic acid is (1:1) - (1:2).
9. A polymeric cement grinding aid made according to the method of any one of claims 1-8.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310177808.6A CN116396447B (en) | 2023-02-28 | 2023-02-28 | Preparation method and application of polymer cement grinding aid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310177808.6A CN116396447B (en) | 2023-02-28 | 2023-02-28 | Preparation method and application of polymer cement grinding aid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN116396447A true CN116396447A (en) | 2023-07-07 |
| CN116396447B CN116396447B (en) | 2024-03-26 |
Family
ID=87014922
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310177808.6A Active CN116396447B (en) | 2023-02-28 | 2023-02-28 | Preparation method and application of polymer cement grinding aid |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116396447B (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101182149A (en) * | 2007-11-19 | 2008-05-21 | 李军 | Composite activated cement reinforced grinding aids containing polycarboxylic acid series and method for preparing the same |
| CN108239243A (en) * | 2017-12-30 | 2018-07-03 | 胡果青 | A kind of preparation method of organic-silicon-modified high-molecular cement grinding aid |
-
2023
- 2023-02-28 CN CN202310177808.6A patent/CN116396447B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101182149A (en) * | 2007-11-19 | 2008-05-21 | 李军 | Composite activated cement reinforced grinding aids containing polycarboxylic acid series and method for preparing the same |
| CN108239243A (en) * | 2017-12-30 | 2018-07-03 | 胡果青 | A kind of preparation method of organic-silicon-modified high-molecular cement grinding aid |
Also Published As
| Publication number | Publication date |
|---|---|
| CN116396447B (en) | 2024-03-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101492518B (en) | Ethers polycarboxylic acid water reducing agent and preparation | |
| JP4146902B2 (en) | Use of polymers containing carboxyl groups and polyalkylene oxide ether-side chains as additives in mineral building materials | |
| US7691982B2 (en) | Dispersant using kraft lignin and novel lignin derivative | |
| JP6031611B2 (en) | Dispersant | |
| US20050131110A1 (en) | Polycarboxylic acid copolymer, production method and use thereof | |
| WO2014085996A1 (en) | Slump retaining polycarboxylic acid superplasticizer | |
| JP2005506436A5 (en) | ||
| CN109627397A (en) | A kind of polycarboxylate water-reducer and preparation method thereof improving cement slurry rheological behavior | |
| CN109650794A (en) | A kind of low slump loss concrete and preparation method thereof | |
| CN108912279B (en) | High-adaptability multi-branched-chain amide imine polycarboxylic water reducer and preparation method thereof | |
| CN112830729B (en) | High-strength concrete and preparation method thereof | |
| CN111704698A (en) | Preparation method of hyperbranched viscosity-reducing polycarboxylate superplasticizer | |
| CN114890759B (en) | 3D printing light material containing wood aggregate and preparation method and application thereof | |
| CN110655620A (en) | Aqueous hyperbranched polyacrylate emulsion, preparation method and application thereof | |
| JPWO2018056124A1 (en) | Additive for cement composition and cement composition | |
| CN116396447B (en) | Preparation method and application of polymer cement grinding aid | |
| JP2003128738A (en) | Polycarboxylic acid-based copolymer, method for producing the same and application of the same | |
| US20010052308A1 (en) | Cement admixture and cement composition comprising this | |
| CN113200703B (en) | Low-air-entraining polycarboxylic acid type water reducing agent and preparation method thereof | |
| CN107935606A (en) | A kind of high-efficiency ceramic base substrate enhancer compositions and its obtained product | |
| CN110627968B (en) | Aqueous organic montmorillonite modifier emulsion, preparation method and application thereof | |
| CN112724340A (en) | Viscosity-reducing composite polycarboxylate superplasticizer and preparation method thereof | |
| CN112279973A (en) | Polycarboxylate superplasticizer for pipe pile and preparation method and application thereof | |
| CN111285979A (en) | Comprehensive dispersing agent capable of adjusting construction time for refractory materials and preparation method thereof | |
| CN114292042B (en) | Preparation method of high-hydrophilicity comb-shaped polymer grafting machine-made sand |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |