CN115819749A - Slump-retaining type polycarboxylate superplasticizer prepared from ester-terminated unsaturated polyether monomer and preparation method thereof - Google Patents
Slump-retaining type polycarboxylate superplasticizer prepared from ester-terminated unsaturated polyether monomer and preparation method thereof Download PDFInfo
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- 239000000178 monomer Substances 0.000 title claims abstract description 65
- 239000004721 Polyphenylene oxide Substances 0.000 title claims abstract description 46
- 229920000570 polyether Polymers 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 229920005646 polycarboxylate Polymers 0.000 title claims description 21
- 239000008030 superplasticizer Substances 0.000 title claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 46
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 29
- 239000002253 acid Substances 0.000 claims abstract description 17
- 239000008367 deionised water Substances 0.000 claims description 18
- 229910021641 deionized water Inorganic materials 0.000 claims description 18
- 239000000243 solution Substances 0.000 claims description 16
- 238000004132 cross linking Methods 0.000 claims description 15
- 239000003054 catalyst Substances 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 12
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 10
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 10
- 239000002994 raw material Substances 0.000 claims description 10
- 125000004185 ester group Chemical group 0.000 claims description 8
- -1 enol ester Chemical group 0.000 claims description 7
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 6
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 6
- 239000003999 initiator Substances 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- 239000007800 oxidant agent Substances 0.000 claims description 6
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 6
- 150000002910 rare earth metals Chemical class 0.000 claims description 6
- 239000002211 L-ascorbic acid Substances 0.000 claims description 5
- 235000000069 L-ascorbic acid Nutrition 0.000 claims description 5
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 5
- 229960005070 ascorbic acid Drugs 0.000 claims description 5
- 230000001590 oxidative effect Effects 0.000 claims description 5
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 claims description 4
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 4
- 229910052746 lanthanum Inorganic materials 0.000 claims description 4
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 3
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethyl mercaptane Natural products CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 238000007151 ring opening polymerisation reaction Methods 0.000 claims description 3
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 claims description 3
- AEUVIXACNOXTBX-UHFFFAOYSA-N 1-sulfanylpropan-1-ol Chemical compound CCC(O)S AEUVIXACNOXTBX-UHFFFAOYSA-N 0.000 claims description 2
- 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 2
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 claims description 2
- PMNLUUOXGOOLSP-UHFFFAOYSA-M 2-sulfanylpropanoate Chemical compound CC(S)C([O-])=O PMNLUUOXGOOLSP-UHFFFAOYSA-M 0.000 claims description 2
- UFQDKRWQSFLPQY-UHFFFAOYSA-N 4,5-dihydro-1h-imidazol-3-ium;chloride Chemical compound Cl.C1CN=CN1 UFQDKRWQSFLPQY-UHFFFAOYSA-N 0.000 claims description 2
- 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 claims description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 2
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 2
- 150000002148 esters Chemical group 0.000 claims description 2
- IMBKASBLAKCLEM-UHFFFAOYSA-L ferrous ammonium sulfate (anhydrous) Chemical compound [NH4+].[NH4+].[Fe+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O IMBKASBLAKCLEM-UHFFFAOYSA-L 0.000 claims description 2
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 claims description 2
- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 claims description 2
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 2
- XWGJFPHUCFXLBL-UHFFFAOYSA-M rongalite Chemical compound [Na+].OCS([O-])=O XWGJFPHUCFXLBL-UHFFFAOYSA-M 0.000 claims description 2
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 claims description 2
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims description 2
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims description 2
- 229940001584 sodium metabisulfite Drugs 0.000 claims description 2
- 235000010262 sodium metabisulphite Nutrition 0.000 claims description 2
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 2
- 229920001225 polyester resin Polymers 0.000 claims 1
- 239000004645 polyester resin Substances 0.000 claims 1
- 230000014759 maintenance of location Effects 0.000 abstract description 2
- 230000010148 water-pollination Effects 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 239000004575 stone Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 4
- 239000004568 cement Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 239000002202 Polyethylene glycol Substances 0.000 description 3
- 230000000740 bleeding effect Effects 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 239000012452 mother liquor Substances 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- 229920000056 polyoxyethylene ether Polymers 0.000 description 3
- 229940051841 polyoxyethylene ether Drugs 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 239000004576 sand Substances 0.000 description 3
- 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 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000007655 standard test method Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- 102220496610 Aryl hydrocarbon receptor nuclear translocator-like protein 1_S10E_mutation Human genes 0.000 description 1
- 239000011398 Portland cement Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000008094 contradictory effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000010881 fly ash Substances 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- QVDTXNVYSHVCGW-ONEGZZNKSA-N isopentenol Chemical compound CC(C)\C=C\O QVDTXNVYSHVCGW-ONEGZZNKSA-N 0.000 description 1
- 125000005394 methallyl group Chemical group 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000012113 quantitative test Methods 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
Classifications
-
- 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
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/91—Use of waste materials as fillers for mortars or concrete
Landscapes
- Macromonomer-Based Addition Polymer (AREA)
Abstract
The invention relates to a slump-retaining polycarboxylic acid water reducing agent prepared from an ester-terminated unsaturated polyether monomer and a preparation method thereof, wherein the structural formula of the ester-terminated unsaturated polyether monomer is as follows:
wherein R is 1 And R 2 Is (CH) 2 ) n N is an integer of 2 to 8; r 3 Is C 1 ‑C 12 A and b are integers of 0 to 100. The ester-terminated unsaturated polyether monomer prepared by the invention has various molecular structures, adjustable hydrophily and lipophilicity and controllable molecular weight, and compared with the traditional slump-retaining polycarboxylic acid water reducing agent, the ester-terminated polyether is gradually hydrolyzed in concrete, so that the prepared water reducing agent has higher retention capacity.
Description
Technical Field
The invention relates to the field of additives, in particular to a slump-retaining type polycarboxylate water reducer prepared from an ester-terminated unsaturated polyether monomer and a preparation method thereof.
Background
The vinyl alcohol macromonomer is used as one of important raw materials for synthesizing the polycarboxylate superplasticizer, and the molecular structure of the macromonomer has very important influence on the synthesis process and the performance of the polycarboxylate superplasticizer. The most common vinyl alcohol macromonomers currently on the market mainly include allyl polyethylene glycol ether (APEG), methallyl polyethylene glycol ether (HPEG), isopentenyl polyethylene glycol ether (TPEG), and the like. Although the macromonomer has simple synthesis process, stable chemical property and good product quality, a plurality of problems also exist. On one hand, in the existing vinyl alcohol macromonomer, most of HPEG and TPEG products account for the existing vinyl alcohol macromonomer, and the structure of the product is relatively single. On the other hand, due to the structural limitation of the traditional polyether macromonomer, the water reducing and slump retaining performance of the polycarboxylic acid water reducing agent cannot be improved. Therefore, the whole industry needs to develop more novel polyether macromonomer varieties to expand the product types and functions of the macromonomers so as to improve the comprehensive performance of the polycarboxylic acid water reducing agent.
Disclosure of Invention
Aiming at the prior art, the invention develops a slump-retaining polycarboxylic acid water reducing agent prepared from an ester-terminated unsaturated polyether monomer and a preparation method thereof, and aims to solve the problems of single polyether monomer structure, poor concrete workability and poor retaining performance.
In this regard, the present invention provides an ester-terminated unsaturated polyether monomer having the following structural formula:
wherein R is 1 And R 2 Is (CH) 2 ) n N is an integer of 2 to 8; r 3 Is C 1 -C 12 A and b are integers of 0 to 100.
Preferably, a and b are integers of 1-70.
Further, the preparation method of the ester group terminated unsaturated polyether monomer comprises the following steps:
under the action of a catalyst, terminal enol ester is taken as an initiator to carry out ring-opening polymerization reaction with ethylene oxide and/or propylene oxide at the temperature of 100-120 ℃ and the pressure of 0.2-0.5MPa, so as to obtain the unsaturated polyether monomer with the ester group end capping.
Preferably, the ring-opening polymerization reaction time is 2 to 4 hours.
Further, the structural formula of the terminal enol ester is as follows:
wherein R is 1 And R 2 Is (CH) 2 ) n N is an integer of 2 to 8; r 3 Is C 1 -C 12 A straight-chain or branched saturated alkyl group.
Further, the using amount of the terminal enol ester is 0.1-15% of the total mass of the raw materials for preparing the ester group terminated unsaturated polyether monomer;
the dosage of the ethylene oxide and/or the propylene oxide is 85-99% of the total mass of the raw materials for preparing the ester group-terminated unsaturated polyether monomer.
Further, the catalyst is a mixture of an alkaline catalyst and a rare earth metal catalyst, and the dosage of the catalyst is 0.01-0.2% of the total mass of the raw materials for preparing the ester group terminated unsaturated polyether monomer;
the alkaline catalyst comprises KOH, naOH and CH 3 At least one of ONa;
the rare earth metal is lanthanum.
The second purpose of the invention is to provide a slump-retaining type polycarboxylate water reducer prepared by ester-terminated unsaturated polyether monomers.
Further, the slump-retaining type polycarboxylate water reducer comprises the following raw materials, by mass, 200 parts of ester-terminated unsaturated polyether monomer, 4-10 parts of crosslinking monomer, 5-12 parts of unsaturated acid, 2-10 parts of functional monomer, 0.2-3 parts of molecular weight regulator, 0.1-2 parts of reducing agent, 0.5-5 parts of oxidant and 150-300 parts of deionized water.
Further, the structural formula of the crosslinking monomer is as follows,
R 4 is (CH) 2 CH 2 O) m M is an integer of 1 to 6;
the structural formula of the functional monomer is as follows:
R 5 is H or CH 3 X is CH 2 Or CH 2 CH 2 。
Further, the unsaturated acid is at least one of acrylic acid, methacrylic acid and itaconic acid;
the reducing agent is at least one of L-ascorbic acid, azodiisopropyl imidazoline hydrochloride, azodicyclohexyl formonitrile, sodium bisulfite, sodium metabisulfite, sodium formaldehyde sulfoxylate, ferrous sulfate heptahydrate and ferrous ammonium sulfate;
the oxidant is at least one of hydrogen peroxide, ammonium persulfate, potassium persulfate and sodium persulfate;
the molecular weight regulator is at least one of mercaptopropionic acid, mercaptoethanol, sodium hypophosphite, mercaptopropanol, mercaptopropionate and p-phenol.
The third purpose of the invention is to provide a preparation method of the slump-retaining type polycarboxylate superplasticizer, which at least comprises the following steps,
s1, dividing deionized water into 3 parts, adding an ester-terminated unsaturated polyether monomer, an oxidant, a crosslinking monomer and a first part of deionized water into a reactor, and stirring and dissolving to obtain a first mixed solution;
s2, taking the functional monomer, the unsaturated acid and the second part of deionized water, and stirring and uniformly mixing to obtain a solution A;
s3, taking the molecular weight regulator, the reducing agent and the third part of deionized water, and uniformly stirring to obtain a solution B;
s4, simultaneously dripping the solution A and the solution B into the first mixed solution under the condition of stirring at normal temperature; and (3) after the dropwise addition is finished, adding alkali to neutralize the pH value to 5-7, thus obtaining the slump-retaining polycarboxylic acid water reducer.
Specifically, the mass ratio of the first part of deionized water to the second part of deionized water to the third part of deionized water is (150-250): 20.
In conclusion, the invention has the following beneficial effects:
1. compared with the traditional slump-retaining type polycarboxylate water reducer, the concrete solution is strongly alkaline along with the hydration of cement, the ester-terminated polyether can be gradually hydrolyzed in an alkaline environment, and the released carboxyl can continuously adsorb and disperse cement particles, so that the concrete can have good fluidity for a long time, and the prepared water reducer has higher retention capacity.
2. According to the invention, a new branched chain structure is introduced into the ester-terminated unsaturated polyether monomer molecule, so that a hydrophobic unit is formed in the water reducing agent, and the problems of poor concrete workability and the like caused by easy bleeding and segregation of the water reducing agent synthesized by the traditional straight-chain monomer are solved, so that the slump retaining performance of the synthesized polycarboxylic acid water reducing agent is greatly improved.
3. According to the invention, the crosslinking monomer is introduced into the molecular structure of the polycarboxylate superplasticizer, so that the prepared polycarboxylate superplasticizer has a micro-crosslinking structure, and can effectively lock water in concrete, thereby further improving the water retention property of the polycarboxylate superplasticizer.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The experimental procedures in the following examples are conventional unless otherwise specified. Test materials, reagents and the like used in the following examples are commercially available unless otherwise specified. In the quantitative tests in the following examples, three replicates were set, and the data are the mean or the mean ± standard deviation of the three replicates.
In addition, "and/or" in the whole text includes three schemes, taking a and/or B as an example, including a technical scheme, and a technical scheme that a and B meet simultaneously; in addition, the technical solutions in the embodiments may be combined with each other, but it must be based on the realization of those skilled in the art, and when the technical solutions are contradictory or cannot be realized, such a combination should not be considered to exist, and is not within the protection scope of the present invention.
Example 1
The preparation method of the ester-terminated unsaturated polyether monomer comprises the following steps:
in a reaction kettle56.5g of initiator, 1.5g of CH were added 3 ONa and 0.06g of rare earth metal lanthanum catalyst, wherein the structural formula of the initiator is as follows: CH (CH) 2 ＝CH-O-CH 2 CH 2 -O-CH 2 CH 2 -OOC-CH 2 CH 3 Controlling the pre-reaction temperature to be 35 ℃ and the pre-reaction time to be 0.8 hour; after the pre-reaction is finished, heating and raising the temperature, keeping the temperature at 90 ℃, vacuumizing, replacing with nitrogen, raising the temperature to 100 ℃, introducing 529g of ethylene oxide, controlling the reaction temperature at 105 ℃ and the pressure at 0.35MPa, reacting until the pressure is not reduced, continuously introducing 331g of propylene oxide, controlling the reaction temperature at 105 ℃ and the pressure at 0.35MPa, and reacting until the pressure is not reduced; after the reaction is finished, cooling to 60 ℃ and discharging to obtain the ester-terminated unsaturated polyether monomer.
A slump retaining type polycarboxylate superplasticizer comprises the following raw materials in parts by weight:
200 parts of ester-group-terminated unsaturated polyether monomer, 5 parts of crosslinking monomer, 5 parts of acrylic acid, 6 parts of allyl glycidyl ether, 1 part of mercaptopropionic acid, 0.5 part of L-ascorbic acid, 2.0 parts of hydrogen peroxide and 220 parts of deionized water.
Wherein, the molecular weight of the ester group terminated unsaturated polyether monomer is 3000, and the structural formula is as follows: CH (CH) 2 ＝CH-O-CH 2 CH 2 -O-CH 2 CH 2 -O-(CH 2 CH 2 O) a -(CH 2 CH 3 CHO) b -OC-CH 2 CH 3 ；
The structural formula of the crosslinking monomer is as follows:
CH 2 ＝CH-O-CH 2 CH 2 O-CH 2 CH 2 O-CH 2 CH 2 O-CH＝CH 2 。
the preparation method of the slump-retaining type polycarboxylate superplasticizer comprises the following steps:
s1, adding an ester-terminated unsaturated polyether monomer, hydrogen peroxide, a crosslinking monomer and 170 parts of deionized water into a reactor, and stirring and dissolving to obtain a first mixed solution;
s2, taking allyl glycidyl ether, acrylic acid and 20 parts of deionized water, and uniformly stirring to obtain a solution A;
s3, taking mercaptopropionic acid, L-ascorbic acid and 30 parts of deionized water, and uniformly stirring to obtain a solution B;
s4, simultaneously dripping the solution A and the solution B into the first mixed solution under the condition of stirring at normal temperature; and (4) after the dropwise addition is finished, adding alkali to neutralize the pH value to 6, thus obtaining the slump-retaining polycarboxylic acid water reducer.
Example 2
The preparation method of the ester-terminated unsaturated polyether monomer comprises the following steps:
adding 76.2g of an initiator, 1.5g of KOH and 0.02g of a rare earth metal lanthanum catalyst into a reaction kettle, wherein the initiator has the structural formula: CH (CH) 2 ＝CH-O-CH 2 CH 2 -O-CH 2 CH 2 -OOC-CH 2 CH 3 Controlling the pre-reaction temperature to be 35 ℃ and the pre-reaction time to be 0.8 hour; after the pre-reaction is finished, heating and raising the temperature, keeping the temperature at 90 ℃, vacuumizing, replacing with nitrogen, raising the temperature to 100 ℃, introducing 1142g of ethylene oxide, controlling the reaction temperature at 105 ℃, and reacting under the pressure of 0.35MPa until the pressure is not reduced; after the reaction is finished, cooling to 60 ℃ and discharging to obtain the ester-terminated unsaturated polyether monomer.
A slump retaining type polycarboxylate superplasticizer comprises the following raw materials in parts by weight:
200 parts of ester-group-terminated unsaturated polyether monomer, 6 parts of crosslinking monomer, 12 parts of acrylic acid, 8 parts of glycidyl methacrylate, 1.5 parts of mercaptoethanol, 0.5 part of L-ascorbic acid, 2.5 parts of hydrogen peroxide and 220 parts of deionized water.
Wherein, the molecular weight of the ester group terminated unsaturated polyether monomer is 3000, and the structural formula is as follows: CH (CH) 2 ＝CH-O-CH 2 CH 2 -O-CH 2 CH 2 -O-(CH 2 CH 2 O) a -OC-CH 2 CH 3 ；
The structural formula of the crosslinking monomer is as follows: CH (CH) 2 ＝CH-O-CH 2 CH 2 O-CH 2 CH 2 O-CH＝CH 2 。
The preparation method of the slump-retaining type polycarboxylate water reducer in the embodiment 2 is the same as that of the embodiment 1.
Comparative example 1 differs from example 1 in that the ester-terminated unsaturated polyether monomer is replaced with the same molecular weight and the same parts by mass of ethylene glycol monovinyl polyoxyethylene ether.
Comparative example 2 differs from example 1 in that no crosslinking monomer is added.
Comparative example 3 differs from example 1 in that no functional monomer is added.
Comparative example 4: the slump retaining agent is S10E slump retaining agent produced by Fujian Limited company, a Jie new material group of the family, and mother liquor of the slump retaining agent is obtained by copolymerizing isopentenol polyoxyethylene ether, acrylic acid and hydroxyethyl acrylate in an oxidation-reduction system. The molecular structural formula of the mother liquor is as follows:
testing of concrete Properties
The concrete mixing ratio is shown in table 1, wherein the cement is Fujian P.O42.5 ordinary portland cement; the machine-made sand is matched with stone powder, the fineness modulus of the machine-made sand is 2.8, the mud content is 4.5 percent, and the powder content is higher; the fineness modulus of the stone powder is 2.7, and the mud content is 14.9%.
TABLE 1 concrete mix proportion (unit: kg/m) 3 )
| Cement | Fly ash | Mineral powder | Stone powder | Machine-made sand | Stone | Water (W) |
| 220 | 50 | 80 | 150 | 780 | 900 | 175 |
The slump-retaining type polycarboxylate superplasticizer prepared in each example and comparative example is prepared according to the following mother liquor: the slump-retaining polycarboxylic acid water reducer is prepared by performing equal-folding and compounding on water = 6.
The test method is used for carrying out performance tests according to GB/T8076-2008 concrete admixture, GB/T50080-2016 standard test method for common concrete mixture performance and GB/T50081-2019 standard test method for physical and mechanical properties of concrete, and the test results are shown in Table 2.
Table 2 results of performance testing
As shown in Table 2, the products of the examples have high water reducing rate, good slump retaining performance, high initial flow rate of concrete, good workability and no bleeding, and the slump retaining performance is obviously reduced after 1 hour by adopting ethylene glycol monoethyl polyoxyethylene ether in the comparative example 1; comparative example 2 no crosslinking monomer was added, the initial state was better, but the loss of concrete was fast 2 h; comparative example 3 no functional monomer was added, the concrete state was significantly worse, exposed stones were significant, and bleeding was more; comparative example 4 lost more rapidly and bleeds more for both 1h and 2 h.
The technical features of the embodiments described above can be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, however, as long as there is no contradiction between the combinations of the technical features, the scope of the present description should be considered as being included in the description of the present specification.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent should be subject to the appended claims.
Claims (10)
1. An ester-terminated unsaturated polyether monomer, wherein the ester-terminated unsaturated polyether monomer has the following structural formula:
wherein R is 1 And R 2 Is (CH) 2 ) n N is an integer of 2 to 8; r 3 Is C 1 -C 12 A and b are integers of 0 to 100.
2. An ester-terminated unsaturated polyether monomer according to claim 1, wherein:
the preparation method of the ester-terminated unsaturated polyether monomer comprises the following steps:
under the action of a catalyst, terminal enol ester is taken as an initiator to carry out ring-opening polymerization reaction with ethylene oxide and/or propylene oxide at the temperature of 100-120 ℃ and under the pressure of 0.2-0.5MPa, so as to obtain the unsaturated polyether monomer with the ester group end capping.
3. An ester-terminated unsaturated polyether monomer according to claim 2, wherein:
the structural formula of the terminal enol ester is as follows:
wherein R is 1 And R 2 Is (CH) 2 ) n N is an integer of 2 to 8; r 3 Is C 1 -C 12 A straight-chain or branched saturated alkyl group.
4. An ester-terminated unsaturated polyether monomer according to claim 2, wherein:
the using amount of the terminal enol ester is 0.1-15% of the total mass of the raw materials for preparing the ester group terminated unsaturated polyether monomer;
the dosage of the ethylene oxide and/or the propylene oxide is 85 to 99 percent of the total mass of the raw materials for preparing the ester-terminated unsaturated polyether monomer.
5. An ester-terminated unsaturated polyether monomer according to claim 2, wherein: the catalyst is a mixture of an alkaline catalyst and a rare earth metal catalyst, and the dosage of the catalyst is 0.01-0.2% of the total mass of the raw materials for preparing the ester-terminated unsaturated polyether monomer;
the alkaline catalyst comprises KOH, naOH and CH 3 At least one of ONa;
the rare earth metal is lanthanum.
6. A slump-retaining polycarboxylic acid water reducing agent, which is characterized by comprising the ester group-terminated unsaturated polyether monomer according to any one of claims 1 to 5.
7. The slump-retaining type polycarboxylate water reducer according to claim 6, characterized in that: the polyester resin comprises, by mass, 200 parts of an ester-terminated unsaturated polyether monomer, 4-10 parts of a crosslinking monomer, 5-12 parts of an unsaturated acid, 2-10 parts of a functional monomer, 0.2-3 parts of a molecular weight regulator, 0.1-2 parts of a reducing agent, 0.5-5 parts of an oxidizing agent and 150-300 parts of deionized water.
8. The slump-retaining type polycarboxylate water reducer according to claim 7, characterized in that:
the structural formula of the crosslinking monomer is shown as follows,
R 4 is (CH) 2 CH 2 O) m M is an integer of 1 to 6;
the structural formula of the functional monomer is as follows:
R 5 is H or CH 3 X is CH 2 Or CH 2 CH 2 。
9. The slump-retaining type polycarboxylate water reducer according to claim 7, characterized in that:
the unsaturated acid is at least one of acrylic acid, methacrylic acid and itaconic acid;
the reducing agent is at least one of L-ascorbic acid, azodiisopropyl imidazoline hydrochloride, azodicyclohexyl formonitrile, sodium bisulfite, sodium metabisulfite, sodium formaldehyde sulfoxylate, ferrous sulfate heptahydrate and ferrous ammonium sulfate;
the oxidant is at least one of hydrogen peroxide, ammonium persulfate, potassium persulfate and sodium persulfate; the molecular weight regulator is at least one of mercaptopropionic acid, mercaptoethanol, sodium hypophosphite, mercaptopropanol, mercaptopropionate and p-phenol.
10. A method for preparing the slump-retaining type polycarboxylate superplasticizer as claimed in claim 7, which is characterized by comprising the following steps: at least comprises the following steps of,
s1, dividing deionized water into 3 parts, adding an ester-terminated unsaturated polyether monomer, an oxidant, a crosslinking monomer and a first part of deionized water into a reactor, and stirring and dissolving to obtain a first mixed solution;
s2, taking the functional monomer, the unsaturated acid and the second part of deionized water, and stirring and uniformly mixing to obtain a solution A;
s3, taking the molecular weight regulator, the reducing agent and the third part of deionized water, and uniformly stirring to obtain a solution B;
s4, simultaneously dripping the solution A and the solution B into the first mixed solution under the condition of stirring at normal temperature; and (3) after the dropwise addition is finished, adding alkali to neutralize the pH value to 5-7, thus obtaining the slump-retaining polycarboxylic acid water reducer.
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