CN117820564A - Production process of polycarboxylate cement water reducer - Google Patents
Production process of polycarboxylate cement water reducer Download PDFInfo
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 107
- 239000003638 chemical reducing agent Substances 0.000 title claims abstract description 75
- 239000000573 polycarboxylate cement Substances 0.000 title claims abstract description 12
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 11
- 238000003756 stirring Methods 0.000 claims abstract description 36
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 34
- 229920000570 polyether Polymers 0.000 claims abstract description 34
- 238000006243 chemical reaction Methods 0.000 claims abstract description 27
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000002253 acid Substances 0.000 claims abstract description 16
- 239000004568 cement Substances 0.000 claims abstract description 15
- 239000011259 mixed solution Substances 0.000 claims abstract description 15
- 239000000178 monomer Substances 0.000 claims abstract description 15
- 229920000056 polyoxyethylene ether Polymers 0.000 claims abstract description 14
- 229940051841 polyoxyethylene ether Drugs 0.000 claims abstract description 14
- HFMLLTVIMFEQRE-UHFFFAOYSA-N 6-amino-1h-pyrimidin-4-one Chemical compound NC1=CC(O)=NC=N1 HFMLLTVIMFEQRE-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000008367 deionised water Substances 0.000 claims abstract description 12
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 12
- 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 11
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229920001911 maleic anhydride grafted polypropylene Polymers 0.000 claims abstract description 11
- 125000005394 methallyl group Chemical group 0.000 claims abstract description 11
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims abstract description 10
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethyl mercaptane Natural products CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 claims abstract description 10
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 claims abstract description 10
- 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 claims abstract description 4
- 229920005646 polycarboxylate Polymers 0.000 claims description 18
- 238000010438 heat treatment Methods 0.000 claims description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 12
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 10
- 239000000243 solution Substances 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- 229920000536 2-Acrylamido-2-methylpropane sulfonic acid Polymers 0.000 claims description 5
- 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 5
- 230000007935 neutral effect Effects 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims 1
- 230000001603 reducing effect Effects 0.000 abstract description 7
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 abstract description 5
- 125000000542 sulfonic acid group Chemical group 0.000 abstract description 4
- 125000003368 amide group Chemical group 0.000 abstract description 3
- 238000002156 mixing Methods 0.000 abstract description 3
- 230000009881 electrostatic interaction Effects 0.000 abstract description 2
- 230000036571 hydration Effects 0.000 abstract description 2
- 238000006703 hydration reaction Methods 0.000 abstract description 2
- 230000002195 synergetic effect Effects 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 20
- 239000004567 concrete Substances 0.000 description 15
- 239000004576 sand Substances 0.000 description 9
- 239000000126 substance Substances 0.000 description 8
- 230000000740 bleeding effect Effects 0.000 description 4
- 238000005189 flocculation Methods 0.000 description 4
- 230000016615 flocculation Effects 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000007792 addition Methods 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- USWINTIHFQKJTR-UHFFFAOYSA-N 3-hydroxynaphthalene-2,7-disulfonic acid Chemical compound C1=C(S(O)(=O)=O)C=C2C=C(S(O)(=O)=O)C(O)=CC2=C1 USWINTIHFQKJTR-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000005204 segregation Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
- XOAAWQZATWQOTB-UHFFFAOYSA-N taurine Chemical compound NCCS(O)(=O)=O XOAAWQZATWQOTB-UHFFFAOYSA-N 0.000 description 2
- 238000012795 verification Methods 0.000 description 2
- FEPBITJSIHRMRT-UHFFFAOYSA-N 4-hydroxybenzenesulfonic acid Chemical compound OC1=CC=C(S(O)(=O)=O)C=C1 FEPBITJSIHRMRT-UHFFFAOYSA-N 0.000 description 1
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 1
- 102000048470 Dixin Human genes 0.000 description 1
- 108700037673 Dixin Proteins 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 150000008064 anhydrides Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000012986 chain transfer agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
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- 238000005260 corrosion Methods 0.000 description 1
- 239000012024 dehydrating agents Substances 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000010881 fly ash Substances 0.000 description 1
- 239000004574 high-performance concrete Substances 0.000 description 1
- 238000009396 hybridization Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
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- 230000004048 modification Effects 0.000 description 1
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- SQMWSBKSHWARHU-SDBHATRESA-N n6-cyclopentyladenosine Chemical compound O[C@@H]1[C@H](O)[C@@H](CO)O[C@H]1N1C2=NC=NC(NC3CCCC3)=C2N=C1 SQMWSBKSHWARHU-SDBHATRESA-N 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- -1 polyoxyethylene Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 230000003335 steric effect Effects 0.000 description 1
- 239000008030 superplasticizer Substances 0.000 description 1
- 229960003080 taurine Drugs 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
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- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention relates to a production process of a polycarboxylate cement water reducer, which belongs to the technical field of water reducers and comprises the following steps: firstly, stirring a mixed solution of 4-amino-6-hydroxypyrimidine, methallyl polyoxyethylene ether, DCC and DMF for reaction to obtain modified polyether; secondly, stirring and reacting the modified polyether, 2-acrylamide-2-methylpropanesulfonic acid and DMF to obtain copolymerized polyether; thirdly, stirring and reacting the copolyether, DMF and maleic anhydride grafted polypropylene to obtain a water reducer monomer; fourthly, mixing and reacting the water reducer monomer, deionized water, acrylic acid, ammonium persulfate, mercaptoethanol and deionized water to obtain the polycarboxylic acid water reducer, wherein the amido of the polycarboxylic acid water reducer can reduce the charge density of the water reducer, the pyridine ring weakens the electrostatic interaction between cement and the water reducer, and the sulfonic acid group is a strong hydration group, so that the mud resistance, the dispersibility and the water reducing performance of the water reducer are improved through the synergistic effect of the sulfonic acid group and the acrylic acid, the ammonium persulfate and the mercaptoethanol.
Description
Technical Field
The invention belongs to the technical field of water reducers, and particularly relates to a production process of a polycarboxylate cement water reducer.
Background
The polycarboxylate water reducer is used as a novel high-performance water reducer, the higher water reducing rate and the working performance maintaining capability can be achieved with a small mixing amount, the chloride ion content in the water reducer is small, the water reducer cannot be replaced by other water reducers in concrete with special requirements on steel bar corrosion, and due to the excellent performance of the polycarboxylate water reducer, the physical and mechanical properties of the hardened concrete are greatly improved, the durability of the concrete can be improved, and the polycarboxylate water reducer is an indispensable raw material in the preparation of high-performance concrete.
The water reducing mechanism of the polycarboxylate water reducer mainly comprises electrostatic repulsion and steric hindrance, when the polycarboxylate water reducer is added into cement paste, the flocculation structure of the cement paste is destroyed, and the water wrapped in the flocculation structure is released to become free water, so that the working performance of the concrete mixture is improved.
Chinese invention CN 114230731B discloses a modified polycarboxylate superplasticizer and a preparation method thereof, comprising the following steps: reacting 2-naphthol-3, 6-disulfonic acid with polyether to obtain modified polyether; adding the modified polyether into water to be dissolved uniformly, adding an oxidant into the water to be stirred uniformly, then adding sodium hypophosphite into the water to be mixed uniformly to obtain solution A, adding water into the unsaturated carboxylic acid to be mixed uniformly to obtain solution B, adding the solution B into the solution A in a dropwise manner, and preserving heat after the dropwise addition is completed to obtain the polycarboxylic acid water reducer with stronger adjustability, lasting water locking property and mud resistance, wherein the dispersing property is not reduced, but the side chain of the water reducer is shorter, so that the water reducer loses huge steric hindrance effect, and the water reducing property of the water reducer is reduced.
Disclosure of Invention
The invention aims to solve the following technical problems:
and the polycarboxylate water reducer with strong mud resistance, good dispersion performance and good water reducing performance is prepared.
The aim of the invention can be achieved by the following technical scheme:
a production process of a polycarboxylic acid cement water reducer comprises the following steps:
adding a mixed solution of 4-amino-6-hydroxypyrimidine, methallyl polyoxyethylene ether, DCC and DMF into a reaction kettle under the protection of nitrogen, stirring for 0.5-1h at the rotating speed of 60-80r/min, heating to 120-150 ℃, adjusting the rotating speed to 240-300r/min, continuing stirring for reacting for 5-6h, and washing and drying to obtain modified polyether;
wherein, the dosage ratio of the 4-amino-6-hydroxy pyrimidine, the methallyl polyoxyethylene ether and the mixed solution is 140-150g:10-20g:500-600mL, and the dosage ratio of DCC and DMF in the mixed solution is 20-25g:500-600mL, taking DCC as a reaction dehydrating agent, and carrying out dehydration condensation reaction on hydrogen on active hydroxyl on a 4-amino-6-hydroxypyrimidine side chain and hydroxyl on methallyl polyoxyethylene ether to obtain modified polyether, wherein the structural formula of the modified polyether is as follows:
secondly, adding modified polyether, 2-acrylamide-2-methylpropanesulfonic acid and DMF into a reaction kettle, stirring for 1-2h at the rotating speed of 80-100r/min, adding azodiisobutyronitrile, heating to 70-75 ℃, adjusting the rotating speed to 400-500r/min, continuing stirring for reacting for 5-6h, and washing and drying to obtain copolymerized polyether;
wherein the dosage ratio of the modified polyether to the 2-acrylamido-2-methylpropanesulfonic acid to the DMF to the azodiisobutyronitrile is 100-150g:20-40g:500-600mL:2-8g, using DMF as solvent and azodiisobutyronitrile as catalyst, so that two double bonds on the modified polyether and double bonds on 2-acrylamido-2-methylpropanesulfonic acid undergo free radical polymerization reaction to obtain copolymerized polyether, wherein the structural formula of the copolymerized methyl ether is shown as follows:
thirdly, adding the copolymerized polyether and DMF into a reaction kettle, stirring for 1-2 hours at the rotating speed of 110-130r/min, adding maleic anhydride grafted polypropylene, heating to 60-70 ℃, adjusting the rotating speed of 600-700r/min, continuing stirring for reacting for 6-7 hours, washing and drying to obtain a water reducer monomer;
wherein, the dosage ratio of the copolymerized polyether to the DMF to the maleic anhydride grafted polypropylene is 50-100g:300-400mL of 25-50g, and DMF is taken as a solvent, and the active amino group on the copolyether can undergo a ring-opening reaction with the anhydride group on the maleic anhydride grafted polypropylene to obtain a water reducer monomer, wherein the structural formula of the water reducer monomer is shown as follows:
fourthly, adding the water reducer monomer and deionized water into a reaction kettle, stirring for 1-2 hours at the rotating speed of 110-130r/min, adding the mixed solution of acrylic acid, ammonium persulfate, mercaptoethanol and deionized water, heating to 60-70 ℃, adjusting the rotating speed to 600-700r/min, continuously stirring for reaction for 6-7 hours, adding 30wt% sodium hydroxide solution to adjust the pH value to be neutral after the reaction is finished, and preserving the temperature for 1-2 hours to obtain the polycarboxylic acid water reducer, wherein the structural formula of the polycarboxylic acid water reducer is shown as follows:
wherein a, b and n are the number of structural units, and m is a polyether structural unit.
Wherein the dosage ratio of the water reducing agent monomer to the mixed solution is 50-100g:80-100mL, wherein the dosage ratio of acrylic acid, ammonium persulfate, mercaptoethanol and deionized water in the mixed solution is 6-12mL:0.55-1g:0.2-0.4mL:20-30mL, acrylic acid is taken as a micromolecular comonomer, ammonium persulfate is taken as an initiator, mercaptoethanol is taken as a chain transfer agent, and the water reducer monomer and acrylic acid undergo free radical copolymerization reaction to obtain the polycarboxylate water reducer.
Further, the maleic anhydride grafted polypropylene is maleic anhydride grafted polypropylene FT900P, the density is 0.90-0.92g/cm3, the melt index is 4-37, and the grafting rate is 1-1.4%.
The invention has the beneficial effects that:
(1) The side chain of the polycarboxylic acid water reducer prepared by the method introduces long-chain copolyamide, sulfonic acid groups and pyridine rings, wherein amide groups in the long-chain copolyamide have strong polarity, hydrogen bonds can be formed in molecules, the charge density of the polycarboxylic acid water reducer is reduced, amide groups are hydrolyzed in an alkaline environment, the number of carboxylic acid groups is increased, cement paste can keep good fluidity, the pyridine rings have rigidity, strong steric hindrance enhances the mud resistance of the polycarboxylic acid water reducer, meanwhile, N in pyridine participates in hybridization, belongs to delocalized large pi bonds and is equivalent to electron-donating groups, electrostatic interaction between the surfaces of cement particles and molecules of the water reducer is weakened, the mud resistance of the polycarboxylic acid water reducer is further enhanced, sulfonic acid groups are strong hydration groups, water can be effectively adsorbed around the side chain of polyether, the dispersion and lubrication performance of the polycarboxylic acid water reducer are improved, meanwhile, the intercalation behavior of the side chain in clay is weakened under the action of the large steric effect of long-chain copolyamide and long-chain polyoxyethylene, and the water reduction performance of the polycarboxylic acid water reducer is further enhanced.
(2) The main chain of the polycarboxylate water reducer is provided with long-chain hydrophobic alkane at two sides, the flocculation structure of cement paste can be destroyed under the action of the large steric hindrance effect, so that water wrapped in the flocculation structure is released to be changed into free water, and meanwhile, terminal carboxyl groups on long-chain alkane chains can form firm electrovalence bond combination with cation areas on the surfaces of cement particles, so that a stable and firm adsorption and winding layer can be formed on the surfaces of the cement particles by polyether chain segments, and the water reducing, isolating and dispersing effects of the polycarboxylate water reducer are further improved.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, 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.
The reagent adopted by the invention is as follows:
4-amino-6-hydroxypyrimidine (99%, chemical intermediate, hubei double-yan chemical Co., ltd.); methallyl polyoxyethylene ether (polyether, molecular weight: 2160-2640, industrial product, nantong Jiuze chemical Co., ltd.); DCC (99%, industrial, dixin chemical limited, zhongshan); DMF (98%, biochemical reagent, jiangsu Pu Le Si Biotechnology Co., ltd.); 2-acrylamide-2-methylpropanesulfonic acid (99.5%, industrial grade, jining Sanshi biotechnology Co., ltd.); azobisisobutyronitrile (99.5%, industrial grade, atactic chemical Co., ltd.); maleic anhydride grafted polypropylene (brand: FT900P, general grade, nanjing Feiteng New Material Co., ltd.); acrylic acid (99%, industrial grade, nantong run Feng petrochemical Co., ltd.); ammonium persulfate (99%, analytically pure, gallery dry technology limited); mercaptoethanol (Jinan Prain chemical Co., ltd.); a common polycarboxylate water reducer (40%, water reduction rate 32%, industrial grade, tianjin smelting special materials Co., ltd.);
and (3) cement: huarun P.O42.5 cement; sand: standard sand, the mud content is set to 0, and the fineness modulus is 2.6-2.9; crushed stone G1: particle size is 20-40mm; containing silt: the machine-made sand of the Texas stirring station contains 12% of mud and has a fineness modulus of 2.7-3.1.
Example 1
The embodiment provides a production process of a polycarboxylate cement water reducer, which comprises the following steps:
in the first step, under the protection of nitrogen, adding 140g of 4-amino-6-hydroxypyrimidine, 10g of methylallyl polyoxyethylene ether, 20g of DCC and 500mL of DMF into a reaction kettle, stirring for 0.5h at the rotating speed of 60r/min, heating to 120 ℃, adjusting the rotating speed of 240r/min, continuing stirring for reacting for 5h, and washing and drying to obtain modified polyether;
adding 100g of modified polyether, 20g of 2-acrylamido-2-methylpropanesulfonic acid and 500mL of DMF into a reaction kettle, stirring for 1h at the rotating speed of 80r/min, adding 2g of azodiisobutyronitrile, heating to 70 ℃, stirring for reacting for 5h at the rotating speed of 400r/min, and washing and drying to obtain copolymerized polyether;
thirdly, adding 50g of copolymerized polyether and 300mL of DMF into a reaction kettle, stirring for 1h at the rotating speed of 110r/min, adding 25g of maleic anhydride grafted polypropylene, heating to 60 ℃, adjusting the rotating speed of 600r/min, continuing stirring for reaction for 6h, and washing and drying to obtain a water reducer monomer;
and fourthly, adding 50g of water reducer monomer and 80mL of deionized water into a reaction kettle, stirring for 1h at the rotating speed of 110r/min, adding a mixed solution of 6mL of acrylic acid, 0.55g of ammonium persulfate, 0.2mL of mercaptoethanol and 20mL of deionized water, heating to 60 ℃, adjusting the rotating speed to 600r/min, continuing stirring for reaction for 6h, adding 30wt% of sodium hydroxide solution to adjust the pH to be neutral after the reaction is finished, and preserving the heat for 1h to obtain the polycarboxylate water reducer.
Example 2
The embodiment provides a production process of a polycarboxylate cement water reducer, which comprises the following steps:
under the protection of nitrogen, adding 150g of 4-amino-6-hydroxypyrimidine, 20g of methylallyl polyoxyethylene ether, 20g of DCC and 600mL of DMF into a reaction kettle, stirring for 1h at the rotating speed of 80r/min, heating to 120-150 ℃, stirring for reacting for 5-6h, washing and drying to obtain modified polyether;
secondly, 150g of modified polyether, 40g of 2-acrylamido-2-methylpropanesulfonic acid and 600mL of DMF are added into a reaction kettle, stirring is carried out for 2 hours at the rotating speed of 100r/min, then 8g of azodiisobutyronitrile is added, the temperature is raised to 75 ℃, the rotating speed is adjusted to 500r/min, stirring reaction is continued for 6 hours, and washing and drying are carried out to obtain copolymerized polyether;
thirdly, adding 100g of copolymerized polyether and 400mL of DMF into a reaction kettle, stirring for 2 hours at the rotating speed of 130r/min, adding 50g of maleic anhydride grafted polypropylene, heating to 70 ℃, adjusting the rotating speed of 700r/min, continuing stirring for reacting for 7 hours, and washing and drying to obtain a water reducer monomer;
and fourthly, adding 100g of water reducer monomer and 100mL of deionized water into a reaction kettle, stirring for 2 hours at the rotating speed of 130r/min, adding a mixed solution of 12mL of acrylic acid, 1g of ammonium persulfate, 0.4mL of mercaptoethanol and 30mL of deionized water, heating to 70 ℃, adjusting the rotating speed to 700r/min, continuing stirring for 7 hours, adding 30wt% of sodium hydroxide solution to adjust the pH to be neutral after the reaction is finished, and preserving the heat for 2 hours to obtain the polycarboxylate water reducer.
Comparative example 1
The comparative example provides a commercial isobutylene polyoxyethylene ether having a relative molecular weight of 2700.
Comparative example 2
This comparative example provides a commercially available 2-aminoethanesulfonic acid.
Comparative example 3
This comparative example provides a commercially available p-hydroxy benzenesulfonic acid.
Comparative example 4
This comparative example provides a commercially available 2-naphthol-3, 6-disulfonic acid.
Comparative example 5
The methallyl polyoxyethylene ether in the first step of example 1 was replaced with the substance of comparative example 1, and 4-amino-6-hydroxypyrimidine was replaced with the substance of comparative example 2, and the remaining raw materials and production process were kept unchanged.
Comparative example 6
The methallyl polyoxyethylene ether in the first step of example 1 was replaced with the substance of comparative example 1, and 4-amino-6-hydroxypyrimidine was replaced with the substance of comparative example 3, and the remaining raw materials and production process were kept unchanged.
Comparative example 7
The methallyl polyoxyethylene ether in the first step of example 1 was replaced with the substance of comparative example 1, and 4-amino-6-hydroxypyrimidine was replaced with the substance of comparative example 4, and the remaining raw materials and production process were kept unchanged.
The modified polycarboxylate water reducers obtained in example 1 and comparative examples 5 to 7 were tested and characterized with a general polycarboxylate water reducer, and specifically as follows:
(1) Slump and expansion degree of concrete are tested according to GB 8076-2008 concrete admixture; and detecting the width of the bleeding ring according to T/CCPA 29-2022 concrete water retention agent, and judging the segregation and bleeding conditions of concrete.
The concrete mix according to table 1 was filled with 0.1% of the normal polycarboxylate water reducer and the modified polycarboxylate water reducer of example 1 (calculated as a cement) respectively, and cured for 28 days in 150mm x 150mm test molds, and the concrete test block was subjected to microstructure test using a hitachi SU8010 high resolution field emission scanning electron microscope.
TABLE 1 concrete mix (kg/m) 3 )
| Cement and its preparation method | Mineral powder | Fly ash | Sand and sand | Stone | Water and its preparation method |
| 170 | 110 | 85 | 810 | 1040 | 173 |
Note that: the sand in the mixing proportion is standard sand and mud-containing sand, and the standard sand is adopted as the dispersion and water retention index of the concrete.
The water retention performance test, namely the segregation of concrete and the severity of bleeding phenomenon, is characterized by the width of a bleeding ring, and the specific result is shown in Table 2.
TABLE 2 influence of Water reducing Agents on Water retention Properties by increasing the addition
As can be seen from Table 2, the polycarboxylic acid water reducers prepared in examples 1 to 2 have stronger water retention properties at the same content of the admixture, relative to comparative examples 5 to 7.
Concrete verification of the mud resistance of the water reducer is shown in table 3.
Table 3 concrete evaluation verification
As can be seen from Table 3, the polycarboxylic acid water reducers prepared in examples 1 to 2 have more excellent mud resistance, good dispersibility and water reducing property than those prepared in comparative examples 5 to 7.
In the description of the present specification, the descriptions of the terms "one embodiment," "example," "specific example," and the like, mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present invention. In this specification, schematic representations of the above terms do not necessarily refer to the same embodiments or examples. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The foregoing is merely illustrative and explanatory of the invention, as various modifications and additions may be made to the particular embodiments described, or in a similar manner, by those skilled in the art, without departing from the scope of the invention or exceeding the scope of the invention as defined in the claims.
Claims (8)
1. The production process of the polycarboxylate cement water reducer is characterized by comprising the following steps of:
adding a mixed solution of 4-amino-6-hydroxypyrimidine, methallyl polyoxyethylene ether, DCC and DMF into a reaction kettle under the protection of nitrogen, stirring for 0.5-1h at the rotating speed of 60-80r/min, heating to 120-150 ℃, adjusting the rotating speed to 240-300r/min, continuing stirring for reacting for 5-6h, and washing and drying to obtain modified polyether;
secondly, adding modified polyether, 2-acrylamide-2-methylpropanesulfonic acid and DMF into a reaction kettle, stirring for 1-2h at the rotating speed of 80-100r/min, adding azodiisobutyronitrile, heating to 70-75 ℃, adjusting the rotating speed to 400-500r/min, continuing stirring for reacting for 5-6h, and washing and drying to obtain copolymerized polyether;
thirdly, adding the copolymerized polyether and DMF into a reaction kettle, stirring for 1-2 hours at the rotating speed of 110-130r/min, adding maleic anhydride grafted polypropylene, heating to 60-70 ℃, adjusting the rotating speed of 600-700r/min, continuing stirring for reacting for 6-7 hours, washing and drying to obtain a water reducer monomer;
and fourthly, adding the water reducer monomer and deionized water into a reaction kettle, stirring for 1-2 hours at the rotating speed of 110-130r/min, adding the mixed solution of acrylic acid, ammonium persulfate, mercaptoethanol and deionized water, heating to 60-70 ℃, adjusting the rotating speed to 600-700r/min, continuously stirring for reaction for 6-7 hours, adding 30wt% sodium hydroxide solution to adjust the pH value to be neutral after the reaction is finished, and preserving the heat for 1-2 hours to obtain the polycarboxylate water reducer.
2. The process for producing the polycarboxylate cement water reducer according to claim 1, wherein in the first step, the dosage ratio of the 4-amino-6-hydroxypyrimidine, the methallyl polyoxyethylene ether and the mixed solution is 140-150g:10-20g:500-600mL.
3. The process for producing the polycarboxylate cement water reducer according to claim 2, wherein the ratio of the DCC to the DMF in the mixed solution is 20-25g:500-600mL.
4. The process for producing the polycarboxylic acid cement water reducer according to claim 1, wherein the dosage ratio of the modified polyether, the 2-acrylamido-2-methylpropanesulfonic acid, the DMF and the azobisisobutyronitrile is 100-150g:20-40g:500-600mL:2-8g.
5. The process for producing a polycarboxylic acid cement water reducing agent according to claim 1, wherein in the third step, the amount ratio of copolymerized polyether, DMF and maleic anhydride grafted polypropylene is 50-100g:300-400mL 25-50g.
6. The process for producing the polycarboxylate cement water reducer according to claim 1, wherein in the fourth step, the dosage ratio of the water reducer monomer to the mixed solution is 50-100g:80-100mL.
7. The process for producing the polycarboxylate cement water reducer according to claim 6, wherein the dosage ratio of the acrylic acid to the ammonium persulfate to the mercaptoethanol to the deionized water in the mixed solution is 6-12mL:0.55-1g:0.2-0.4mL:20-30mL.
8. The process for producing the polycarboxylate cement water reducer according to claim 1, wherein the methallyl polyoxyethylene ether is of an industrial grade, the molecular weight is 2160-2640, the moisture content is less than 1%, the hydroxyl value is 21-26mgKOH/g, the unsaturation degree is more than or equal to 0.37mmol/g, and the pH of a 1% aqueous solution is 5-7.
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