CN114644759B - Small-molecular phosphorous acid-based water reducing agent, and preparation method and application thereof - Google Patents
Small-molecular phosphorous acid-based water reducing agent, and preparation method and application thereof Download PDFInfo
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- CN114644759B CN114644759B CN202011517526.9A CN202011517526A CN114644759B CN 114644759 B CN114644759 B CN 114644759B CN 202011517526 A CN202011517526 A CN 202011517526A CN 114644759 B CN114644759 B CN 114644759B
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- reducing agent
- water reducing
- reaction
- polyamine
- phosphite
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 155
- 239000003638 chemical reducing agent Substances 0.000 title claims abstract description 125
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 50
- 229920000570 polyether Polymers 0.000 claims abstract description 50
- 125000003368 amide group Chemical group 0.000 claims abstract description 39
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 32
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 32
- 150000001990 dicarboxylic acid derivatives Chemical group 0.000 claims abstract description 30
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims abstract description 29
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical group OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 15
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 claims abstract description 15
- 238000001179 sorption measurement Methods 0.000 claims abstract description 12
- 230000009471 action Effects 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims description 97
- 229920000768 polyamine Polymers 0.000 claims description 72
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 54
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 40
- 239000004568 cement Substances 0.000 claims description 24
- 239000000203 mixture Substances 0.000 claims description 24
- 238000007098 aminolysis reaction Methods 0.000 claims description 23
- 239000007864 aqueous solution Substances 0.000 claims description 22
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 16
- 125000004432 carbon atom Chemical group C* 0.000 claims description 16
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 14
- 238000010992 reflux Methods 0.000 claims description 14
- 150000005690 diesters Chemical class 0.000 claims description 12
- 239000000178 monomer Substances 0.000 claims description 12
- 239000003054 catalyst Substances 0.000 claims description 11
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 claims description 10
- 150000001335 aliphatic alkanes Chemical group 0.000 claims description 10
- 150000001336 alkenes Chemical group 0.000 claims description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- 229910019142 PO4 Inorganic materials 0.000 claims description 8
- 150000007942 carboxylates Chemical group 0.000 claims description 8
- 239000010452 phosphate Substances 0.000 claims description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 7
- 238000005731 phosphitylation reaction Methods 0.000 claims description 7
- 239000011230 binding agent Substances 0.000 claims description 6
- 229940098779 methanesulfonic acid Drugs 0.000 claims description 6
- 150000003384 small molecules Chemical class 0.000 claims description 6
- 238000006482 condensation reaction Methods 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 5
- 239000003513 alkali Substances 0.000 claims description 4
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 claims description 4
- 229940092714 benzenesulfonic acid Drugs 0.000 claims description 4
- VHRGRCVQAFMJIZ-UHFFFAOYSA-N cadaverine Chemical compound NCCCCCN VHRGRCVQAFMJIZ-UHFFFAOYSA-N 0.000 claims description 4
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims description 4
- 230000003472 neutralizing effect Effects 0.000 claims description 4
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 claims description 4
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 claims description 4
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 3
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 3
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 3
- YMHQVDAATAEZLO-UHFFFAOYSA-N cyclohexane-1,1-diamine Chemical compound NC1(N)CCCCC1 YMHQVDAATAEZLO-UHFFFAOYSA-N 0.000 claims description 3
- 239000010440 gypsum Substances 0.000 claims description 3
- 229910052602 gypsum Inorganic materials 0.000 claims description 3
- LSHROXHEILXKHM-UHFFFAOYSA-N n'-[2-[2-[2-(2-aminoethylamino)ethylamino]ethylamino]ethyl]ethane-1,2-diamine Chemical compound NCCNCCNCCNCCNCCN LSHROXHEILXKHM-UHFFFAOYSA-N 0.000 claims description 3
- 238000006386 neutralization reaction Methods 0.000 claims description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 3
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims description 2
- 235000011941 Tilia x europaea Nutrition 0.000 claims description 2
- 239000012445 acidic reagent Substances 0.000 claims description 2
- 239000000654 additive Substances 0.000 claims description 2
- 230000000996 additive effect Effects 0.000 claims description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims description 2
- 238000010790 dilution Methods 0.000 claims description 2
- 239000012895 dilution Substances 0.000 claims description 2
- 239000002270 dispersing agent Substances 0.000 claims description 2
- 239000010881 fly ash Substances 0.000 claims description 2
- 239000004571 lime Substances 0.000 claims description 2
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 claims description 2
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 claims description 2
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 claims description 2
- 239000002893 slag Substances 0.000 claims description 2
- 238000006561 solvent free reaction Methods 0.000 claims description 2
- 239000004567 concrete Substances 0.000 abstract description 22
- 239000004927 clay Substances 0.000 abstract description 10
- 230000000694 effects Effects 0.000 abstract description 8
- 150000001733 carboxylic acid esters Chemical group 0.000 abstract description 3
- 238000010438 heat treatment Methods 0.000 description 37
- 238000003756 stirring Methods 0.000 description 29
- 238000001816 cooling Methods 0.000 description 24
- 238000012360 testing method Methods 0.000 description 19
- 239000000243 solution Substances 0.000 description 18
- 238000005227 gel permeation chromatography Methods 0.000 description 16
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 13
- 238000009826 distribution Methods 0.000 description 12
- 229910052739 hydrogen Inorganic materials 0.000 description 10
- 239000002253 acid Substances 0.000 description 9
- -1 alkyl glycoside Chemical class 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 6
- 229920005646 polycarboxylate Polymers 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 230000000979 retarding effect Effects 0.000 description 6
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 5
- MGJURKDLIJVDEO-UHFFFAOYSA-N formaldehyde;hydrate Chemical compound O.O=C MGJURKDLIJVDEO-UHFFFAOYSA-N 0.000 description 5
- 230000036571 hydration Effects 0.000 description 5
- 238000006703 hydration reaction Methods 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 239000004570 mortar (masonry) Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 239000004576 sand Substances 0.000 description 5
- 230000035945 sensitivity Effects 0.000 description 5
- 239000008030 superplasticizer Substances 0.000 description 5
- 150000001408 amides Chemical class 0.000 description 4
- 230000003111 delayed effect Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 3
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000033228 biological regulation Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910001424 calcium ion Inorganic materials 0.000 description 2
- 125000002843 carboxylic acid group Chemical group 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 125000004185 ester group Chemical group 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 238000005086 pumping Methods 0.000 description 2
- 238000010526 radical polymerization reaction Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 229960001124 trientine Drugs 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- ATVJXMYDOSMEPO-UHFFFAOYSA-N 3-prop-2-enoxyprop-1-ene Chemical compound C=CCOCC=C ATVJXMYDOSMEPO-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229920002873 Polyethylenimine Polymers 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 238000005576 amination reaction Methods 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- QVYARBLCAHCSFJ-UHFFFAOYSA-N butane-1,1-diamine Chemical compound CCCC(N)N QVYARBLCAHCSFJ-UHFFFAOYSA-N 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000011083 cement mortar Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- IDAGXRIGDWCIET-SDFKWCIISA-L disodium;(2s,3s,4s,5r)-2,3,4,5-tetrahydroxyhexanedioate Chemical compound [Na+].[Na+].[O-]C(=O)[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O IDAGXRIGDWCIET-SDFKWCIISA-L 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 239000005357 flat glass Substances 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 229930182470 glycoside Natural products 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- GGHDAUPFEBTORZ-UHFFFAOYSA-N propane-1,1-diamine Chemical compound CCC(N)N GGHDAUPFEBTORZ-UHFFFAOYSA-N 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000013268 sustained release Methods 0.000 description 1
- 239000012730 sustained-release form Substances 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block 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
- C04B24/24—Macromolecular compounds
- C04B24/243—Phosphorus-containing polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/335—Polymers modified by chemical after-treatment with organic compounds containing phosphorus
- C08G65/3356—Polymers modified by chemical after-treatment with organic compounds containing phosphorus having nitrogen in addition to phosphorus
-
- 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
- C04B2103/30—Water reducers, plasticisers, air-entrainers, flow improvers
-
- 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
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Polymers & Plastics (AREA)
- Medicinal Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Structural Engineering (AREA)
- Polyethers (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
The invention discloses a micromolecule phosphorous acid-based water reducing agent, a preparation method and application thereof. The structure of the water reducing agent has phosphorous acid groups, carboxylic ester groups and amide groups, firstly polyethylene glycol is introduced into a dicarboxylic acid derivative structure, the molecular structure of the water reducing agent takes the dicarboxylic acid derivative as a bridging group, phosphorous acid groups are introduced as adsorption groups, and finally the water reducing agent is condensed with methoxy polyether to obtain the micromolecule phosphite water reducing agent simultaneously containing the carboxylic ester groups and the amide groups. The micromolecular phosphate group water reducing agent prepared by the method has good slump retaining capacity under the condition of low doping amount, and has stronger action effect and adaptability. More importantly, the invention can realize that the working performance and the concrete workability can be kept good under the condition of higher clay content.
Description
Technical Field
The invention belongs to the field of preparation of concrete admixtures, and particularly relates to a preparation method of a micromolecule phosphate group water reducing agent with strong slump retaining and slow-setting performances.
Background
The concrete water reducing agent is the simplest, most effective and most economic technical means for reducing the cement consumption of concrete, improving the utilization rate of industrial waste residues and improving the strength, the working performance and the durability of the concrete, and is a necessary material and a core technology for modern concrete preparation.
The polycarboxylate superplasticizer is used as a third-generation high-performance water reducing agent, and is mainly prepared by carrying out free radical polymerization reaction on unsaturated carboxylic acid and unsaturated polyether macromonomer to obtain a polymer with a comb-shaped structure, wherein a carboxylic acid adsorption group on a main chain of the polymer provides electrostatic repulsion, and a polyether side chain can provide effective steric hindrance. Compared with the traditional sulfonate water reducing agent, the polycarboxylic acid water reducing agent has more excellent performance in the aspects of water reducing performance, workability, slump loss resistance and the like.
However, with the continuous popularization and use of polycarboxylic acid series products, the share of the polycarboxylic acid water reducing agent is continuously enlarged, which puts new higher requirements on the performance of the polycarboxylic acid water reducing agent, and not only needs the polycarboxylic acid water reducing agent to have good dispersing capacity, but also needs special requirements on good slump retention, workability, retardation, clay tolerance and the like. Theoretical research and engineering application show that the polycarboxylate superplasticizer has compatibility with concrete materials, and has the phenomena of quick concrete slump loss, abnormal coagulation, slow strength increase, shrinkage increase, easy cracking and the like. These phenomena indicate that it is difficult to satisfy the various demands of the market by relying solely on the conventional polycarboxylic acid water reducing agent.
Patent CN101205127B reports a preparation method of a sustained-release type polycarboxylate superplasticizer. Firstly, polyether and maleic anhydride are esterified to obtain an unsaturated esterified intermediate, then the unsaturated esterified intermediate is subjected to free radical polymerization with acrylic acid, maleic anhydride and the like to obtain a finished product of the water reducing agent, and the water reducing agent can continuously release new carboxylic acid adsorption groups through hydrolysis of anhydride or ester in the structure, so that the effects of reducing water and protecting slump are achieved. Patent US5162402 also reports a similar slump retaining agent synthesized from allyl ether and maleic anhydride esterified compound, and also has excellent slump retaining performance.
Patent CN101066851B reports a polycarboxylate concrete slump retaining agent. The unsaturated carboxylic acid monomer and the unsaturated ester polyether macromonomer are crosslinked by using a crosslinking agent to prepare a finished product with a certain crosslinking degree. The water reducing agent can be compounded with other carboxylic acid water reducing agents for use, so that the slump loss of the water reducing agent is improved, and the adaptability of the water reducing agent to cement types, gypsum forms, concrete mixing processes and the like is improved. Patents US5362324, US5661206, etc. report similar polymers prepared by ester crosslinking technology, and the slump retaining performance is improved by continuous hydrolysis of ester groups in the polymer structure.
Wang Ziming research group (preparation and performance of novel amide polyamine polycarboxylate superplasticizer [ Master thesis ], 2009) developed a class of amide polyamine polycarboxylate superplasticizers. The introduction of the amide polyamine unit can promote adsorption, so that the water reducing agent is more easily adsorbed to the surface of cement particles, and the water reducing agent obtains larger early fluidity; the amide groups of the water reducing agent can form a large number of hydrogen bonds with water, the thickness of a hydration film is increased, the hydration of cement is delayed, and meanwhile, nitrogen atoms containing lone pair electrons in the structure can play a role of complexing calcium ions to form a calcium-rich protective layer, so that the hydration of the cement is delayed, and the retarding and slump-retaining performances of the water reducing agent are greatly improved.
Patent CN103449749 reports a high temperature resistant super retarder with good dispersion performance and a preparation method thereof. The organic phosphate/acrylate/carboxylate/sulfonate/nonionic terpolymer and the alkyl glycoside surfactant are compounded according to a certain proportion. Solves the problem of high-temperature adaptability of the retarder, and can be compounded with various water reducing agents for use.
The slump retaining performance of the water reducing agent is improved by the development work on the aspects of slump retaining and slow setting performance of the water reducing agent or by releasing new carboxylic acid groups through continuous hydrolysis of ester groups; or by introducing amide groups, the hydration process of the cement is delayed, and the slump retaining and set retarding performance of the water reducing agent is enhanced; or the retarding effect of the water reducing agent is improved by introducing a compound containing phosphoric acid groups.
Research work that has been carried out at present shows that the role of the phosphate group is not limited to retardation, and the phosphate group grafted onto the polyether chain can realize the performances such as slump retention, water reduction and the like.
Patent US5879445 discloses a small molecular water reducing agent, which takes monoamino polyether as a raw material, and the monoamino polyether is reacted with formaldehyde and phosphorous acid through mannich to prepare polyether derivatives with double phosphorous acid groups at the tail ends, and the polyether derivatives show obvious retardation effect and certain water reducing performance.
Ran Qianping and the like (Synthesis, catalysis and dispersion properties of a series of bis (phosphorus acid) amino-terminated polymers [ J ]. Colloid.Polym.Sci.,2016,294, 189-194) carry out a phosphorous acidation reaction on amino polyether, and a series of phosphorous acid group-containing low molecular weight polyether derivatives are synthesized, which show good slump retaining and water reducing performances and have low sensitivity to clay. Patent CN105504297a reports a phosphorous acid concrete superplasticizer with polyethyleneimine structure. The polyether derivative can be used alone or in combination with a sulfonate water reducer, a polycarboxylic acid water reducer and the like, and can effectively improve the flowing property and slump retaining property of concrete.
The polyether derivative obtained by introducing phosphorous acid groups into a polyether structure not only has certain steric hindrance, but also has stronger adsorption capacity than carboxylic acid groups and sulfonic acid groups, so the polyether derivative not only has obvious slump retaining performance and a retarding effect, but also has certain water reducing performance. However, the aminopolyethers used in the polyether derivatives are mainly obtained by two ways, one is that after the methoxypolyethers are chlorinated, the aminopolyethers are aminated, chloride ions are introduced by the method, and the concrete industry has strict regulations on the content of the chloride ions; the second mode is direct amination of methoxy polyether, only a few companies master industrialized methods at present, and the aminated methoxy polyether is high in cost and poor in economical efficiency.
In addition, the polyether derivative containing the phosphoric acid group only contains the phosphoric acid adsorption group, and does not have a group structure which releases other adsorption groups at the later stage, and the slump retaining performance of the polyether derivative is improved by retarding the slump retaining performance of the water reducer by supposing that the slump retaining effect of the polyether derivative is similar to the effects of sodium saccharate, polysaccharide and the like.
The invention aims to develop a micromolecule water reducing agent which has a more novel structure and has phosphite groups, carboxylate groups and amide groups, and the water reducing agent not only has strong slump retaining and slow setting performances, but also has lower sensitivity in clay.
Disclosure of Invention
Aiming at the problems in the background art, the invention aims to develop a novel structure, and a sample obtained under the structure has multiple performances.
In order to achieve the purpose, the invention provides a micromolecule phosphite water reducing agent, the structure of which has phosphite groups, carboxylate groups and amide groups, firstly polyethylene glycol is introduced into the structure of dicarboxylic acid derivatives, the molecular structure of the water reducing agent takes the dicarboxylic acid derivatives as bridging groups, phosphorous acid groups are introduced as adsorption groups, and finally the water reducing agent is condensed with methoxy polyether to obtain the micromolecule phosphite water reducing agent simultaneously containing carboxylate groups and amide groups.
The invention also provides a preparation method of the micromolecular phosphate group water reducing agent, which comprises the following steps:
(1) And (3) aminolysis reaction: carrying out aminolysis reaction on polyamine monomer and polyethylene glycol dicarboxylic acid derivative mono/diester to obtain polyamine intermediate containing an amide structure;
(2) And (3) carrying out a phosphitylation reaction: reacting the polyamine intermediate containing the amide structure with formaldehyde and phosphorous acid to obtain a hypophosphorous polyamine intermediate;
(3) Preparing a micromolecular phosphate group water reducing agent: carrying out condensation reaction on the phosphorylated polyamine intermediate and a methoxy polyether macromonomer to obtain a phosphite micromolecule water reducing agent;
in the step (1), the molar ratio of the polyamine monomer to the polyethylene glycol dicarboxylic acid derivative mono/diester is 1:1.05-1.5;
in the step (1), the polyamine monomer is selected from more than one of ethylenediamine, propylenediamine, butylenediamine, pentylenediamine, hexylenediamine, cyclohexanediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine and polyethylene polyamine, and is mixed in any proportion;
the structural formula of the polyethylene glycol dicarboxylic acid derivative mono/diester in the step (1) is shown as the formula (I):
wherein R1 is alkane, alkene and derivatives thereof containing 2-10 carbon atoms, and preferably R1 is selected from alkane or alkene containing 2-5 carbon atoms; x, Y is independently selected from H or- (CH) 2 CH 2 O) n -H, and X, Y at least one of which is- (CH) 2 CH 2 O) n -H structure, n is an integer from 3 to 12;
the mono/diester of the polyethylene glycol dicarboxylic acid derivative is obtained from polyethylene glycol and a dicarboxylic acid derivative, and the esterification means is well known in the art and is not described more;
the molar ratio of the polyamine intermediate containing the amide structure, the phosphorous acid and the formaldehyde in the step (2) is 1 (2m + p) to (2m + p), wherein m and p respectively represent the number of nitrogen atoms of a primary amino group and a secondary amino group in the polyamine intermediate;
the molar ratio of the methoxy polyether macromonomer in the step (3) to the polyethylene glycol dicarboxylic acid derivative mono/diester in the step (1) is 1:1; the polyether chain of the methoxy polyether macromonomer is pure ethylene oxide or a mixture of ethylene oxide and propylene oxide, and the weight average molecular weight is preferably 1000-5000.
The preparation method of the micromolecule phosphate group water reducing agent specifically comprises the following steps:
(1) And (3) aminolysis reaction: polyamine monomer and polyethylene glycol dicarboxylic acid derivative mono/diester are subjected to aminolysis reaction under certain pressure and temperature conditions to obtain polyamine intermediate containing an amide structure;
(2) And (3) carrying out a phosphitylation reaction: adding formaldehyde and phosphorous acid into a product obtained in the step (1), and reacting the polyamine intermediate containing the amide structure obtained in the step (1) with formaldehyde and phosphorous acid under a certain condition under the action of a catalyst to obtain a hypophosphorylated polyamine intermediate;
(3) Preparing a micromolecular phosphate group water reducing agent: and (3) adding a methoxy polyether macromonomer into the product obtained in the step (2), and carrying out condensation reaction on the hypophosphorous polyamine intermediate obtained in the step (2) and the methoxy polyether macromonomer under a certain condition to obtain the micromolecule phosphite-based water reducing agent.
The reaction in the step (1) is a solvent-free reaction, the reaction temperature is 120-160 ℃, the reaction pressure is the self pressure of the reaction system, and the reaction time is 6-15 h;
the step (2) is a phosphitylation reaction of polyamine intermediate containing an amide structure, which has been reported in various patents and is well known to practitioners in the art; the reaction temperature in the step (2) is 90-140 ℃, and the reaction time is 5-14 h;
the catalyst in the step (2) is a strong acid reagent selected from one or a mixture of more of concentrated hydrochloric acid, concentrated sulfuric acid, methanesulfonic acid, trifluoromethanesulfonic acid, benzenesulfonic acid and p-methanesulfonic acid; in the reaction in the step (2), in order to ensure the effect of the phosphitylation reaction, the amount of the catalyst is generally equal to the mass of the polyamine monomer in the step (1); a condenser (pipe) reflux device is required to be installed in the reaction device used in the step (2), so that the loss of system acid or formaldehyde is prevented, and the reaction effect is prevented from being influenced;
the reaction temperature in the step (3) is 80-120 ℃, the reaction time is 5-10 h, and the reaction pressure is negative pressure condition of-0.05 MPa to-0.1 MPa;
no additional catalyst is required to be added in the reaction in the step (3), and the catalyst in the step (2) can be continuously used as the catalyst in the step (3);
adding alkali into the micromolecule phosphorous acid-based water reducing agent for neutralization in the step (3), and adding water for dilution to a certain concentration to obtain a finished product of the water reducing agent; adding alkali to neutralize, wherein a NaOH aqueous solution with the mass fraction of 30% is generally used for neutralizing the reaction system to PH =7; and then adding water to dilute to a certain concentration, and generally adding water to dilute the water reducing agent to the mass concentration of about 30-50% for the purposes of storage and transportation.
The invention relates to the use of the small molecule phosphate group water reducing agent as a water dispersant for hydraulic binders and/or latent hydraulic binders;
the small molecular phosphorous acid-based water reducing agent is used as an additive for cement, lime, gypsum or anhydrous gypsum or a mixture of the components, preferably cement. The latent hydraulic binder is typically present in the form of a pozzolan, fly ash or blast furnace slag.
The micromolecular phosphate group water reducing agent prepared by the method has good slump retaining capacity under the condition of low doping amount, and has stronger action effect and adaptability. More importantly, the invention can realize that the working performance and the concrete workability can be kept well under the condition of higher clay content.
The invention has the following beneficial effects:
(1) The dicarboxylic acid derivative is used as a bridging group, so that a carboxylic ester group and an amide group are simultaneously introduced into the structure of the water reducing agent; the polyethylene glycol is creatively introduced into the structure of the dicarboxylic acid derivative, the polyethylene glycol is beneficial to the aminolysis reaction, and the polyethylene glycol can be used as a solvent subsequently to avoid the unfavorable result that the dicarboxylic acid derivative directly reacts with the polyamine to form a thick paste.
(2) Phosphorous acid groups are introduced into the structure of the water reducing agent as adsorption groups, because bidentate phosphoric acid has stronger coordination capacity, can be more quickly adsorbed to the surface of cement particles, shows stronger environmental adaptability of cement and high sulfate and low clay sensitivity, has great performance advantages under the market environment with poor quality of the current concrete admixture and aggregate, and can be developed into a core technology.
(3) The structure of the micromolecule water reducing agent has both carboxylate groups or amide groups, so that new carboxyl adsorption groups can be continuously released at the later adsorption stage, or the hydration process of cement is delayed through the hydrogen bond action of amide and water and the complex calcium ion action of nitrogen atoms, and better retarding and slump retaining performances are achieved.
(4) The process has the advantages of low cost of selected raw materials, simple and efficient synthesis process, low production energy consumption and industrial prospect.
Detailed Description
The present invention is described in detail below by way of examples, which are intended to be illustrative only and not to be construed as limiting the scope of the invention, and one skilled in the art will be able to make variations within the scope of the invention based on the disclosure herein, in reagents, catalysts and reaction process conditions. All equivalent changes or modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.
In the examples of the present invention, the number average molecular weight of the polymer was measured by Wyatt technology corporation gel permeation chromatography. (gel column: shodex SB806+803 two chromatographic columns in series; eluent: 0.1M NaNO 3 A solution; velocity of mobile phase: 0.8ml/min; and (3) injection: 20 μ l of 0.5% aqueous solution; a detector: a refractive index detector of Shodex RI-7 type; standard substance: polyethylene glycol GPC standard (Sigma-Aldrich, molecular weight 1010000,478000,263000,118000,44700,18600,6690,1960,628,232)
In the application embodiment of the invention, the adopted cement is reference cement (P.042.5) except for special description, the sand is medium sand with fineness modulus Mx =2.6, and the stones are continuous graded broken stones with the grain size of 5-20 mm. The fluidity test of the cement paste is carried out according to the GB/T8077-2000 standard, the water adding amount is 87g, and the fluidity of the cement paste is measured on plate glass after stirring for 3 min. The test method of the gas content and the water reducing rate is carried out according to the relevant regulations of GB8076-2008 concrete admixture. Slump and slump loss were performed according to the instructions of JC473-2001, concrete pumping aid.
In the embodiment, the parts are specifically parts by mass, and the addition amount of other materials is converted into parts by mass.
Example 1
(1) Aminolysis reaction
189.3 parts of tetraethylenepentamine and polyethylene glycol dicarboxylic acid derivative monoester (R1 in the structural formula I is alkane with 2 carbon atoms, X, Y is respectively H, - (CH) 2 CH 2 O) n -H, n = 5) placing 405.6 parts of the polyamine into a reaction kettle, heating to 145 ℃, stirring and reacting for 10 hours to obtain the polyamine intermediate containing the amide structure after the reaction is finished.
(2) Phosphorous acidation reaction
And continuously adding 492.0 parts of phosphorous acid into the reaction kettle, adding 189.3 parts of concentrated sulfuric acid while stirring, heating to 90 ℃, keeping for 5min, then dropwise adding 487.0 parts of 37wt% formaldehyde aqueous solution, installing a condensing tube, heating for reflux reaction for 10h, and cooling to obtain a hypophosphorylated polyamine intermediate.
(3) Preparation of water reducing agent
Continuously adding 1200 parts of methoxy polyether (Mw 1000, formed by polymerization of pure ethylene oxide) into the reaction kettle, heating to 80 ℃ under the negative pressure condition of-0.05 MPa to-0.1 MPa, and stirring for reaction for 6 hours; after cooling, the mixture is neutralized by NaOH aqueous solution until the pH is =7, and the mixture is diluted by adding water to 30wt% of water reducing agent solution, so that a reddish brown water reducing agent finished product is obtained, and the weight average molecular weight is 2060 and the molecular weight distribution is 1.08 according to GPC test.
Example 2
(1) Aminolysis reaction
116.2 parts of hexamethylene diamine and polyethylene glycol dicarboxylic acid derivative diester (R1 in the structural formula I is olefin with 4 carbon atoms, X, Y are both- (CH) 2 CH 2 O) n And (3) placing 5363 parts of 1167.6 into a reaction kettle, heating to 120 ℃, stirring and reacting for 7.5 hours to obtain the polyamine intermediate containing the amide structure after the reaction is finished.
(2) Phosphorous acidation reaction
And continuously adding 246 parts of phosphorous acid into the reaction kettle, adding 116.2 parts of methanesulfonic acid while stirring, heating to 125 ℃, keeping for 5min, then dropwise adding 243.5 parts of 37wt% formaldehyde water solution, installing a condensing tube, heating and refluxing for 13h, and cooling to obtain a hypophosphorous polyamine intermediate.
(3) Preparation of water reducing agent
Continuously adding 675 parts of methoxy polyether (Mw 3500, which is formed by copolymerizing ethylene oxide and propylene oxide and the molar ratio of the propylene oxide is 0.05) into the reaction kettle, heating to 115 ℃ under the negative pressure condition of-0.05 MPa to-0.1 MPa, and stirring for reaction for 7.5 hours. After cooling, the mixture is neutralized by NaOH aqueous solution until the pH is =7, and water is added to dilute the mixture to 30wt% of water reducing agent solution, so that a reddish brown water reducing agent finished product is obtained, and the weight average molecular weight is 4192 and the molecular weight distribution is 1.06 according to GPC test.
Example 3
(1) Aminolysis reaction
103.2 parts of diethylenetriamine and polyethylene glycol dicarboxylic acid derivative monoester (R1 in the structural formula I is alkane with 3 carbon atoms, X, Y are respectively H, - (CH) 2 CH 2 O) n And (3) placing 5363 parts of 431.2 in a reaction kettle, heating to 136 ℃, stirring for reacting for 9H, and obtaining the polyamine intermediate containing the amide structure after the reaction is finished.
(2) Phosphorous acidation reaction
And continuously adding 328 parts of phosphorous acid into the reaction kettle, adding 103.2 parts of trifluoromethanesulfonic acid while stirring, heating to 110 ℃, keeping for 5min, then dropwise adding 324.6 parts of 37wt% formaldehyde aqueous solution, installing a condensing tube, heating and refluxing for 6h, and cooling to obtain a hypophosphorous polyamine intermediate.
(3) Preparation of water reducing agent
Continuously adding 2800 parts of methoxy polyether (Mw 2000, ethylene oxide and propylene oxide are copolymerized, and the molar ratio of the propylene oxide is 0.10) into the reaction kettle, heating to 90 ℃ under the negative pressure condition of-0.05 MPa to-0.1 MPa, and stirring for reaction for 9 hours; after cooling, the mixture is neutralized by NaOH aqueous solution until PH =7, and the mixture is diluted by water to 30wt% of water reducing agent solution, so that a reddish brown finished water reducing agent product is obtained, and through GPC test, double peaks appear, the weight average molecular weight is 4679 and 2581 respectively, the molecular weight distribution is 1.07 and 1.04 respectively, and the area ratio of the two peaks is 2:3.
Example 4
(1) Aminolysis reaction
88.2 portions of butanediamine and polyethylene glycol dicarboxylic acid derivative monoester (R1 in the structural formula I is olefin with 5 carbon atoms, X, Y is respectively H, - (CH) 2 CH 2 O) n -H, n = 7) 582.5 parts of the polyamine intermediate are placed in a reaction kettle, the temperature is raised to 160 ℃, the reaction is stirred for 8 hours, and the polyamine intermediate containing the amide structure is obtained after the reaction is finished.
(2) Phosphorous acidation reaction
And continuously adding 246 parts of phosphorous acid into the reaction kettle, adding 88.2 parts of p-toluenesulfonic acid under stirring, heating to 105 ℃, keeping for 5min, then dropwise adding 243.5 parts of 37wt% formaldehyde aqueous solution, installing a condensing tube, heating and refluxing for 11h, and cooling to obtain a phosphitylated polyamine intermediate.
(3) Preparation of water reducing agent
Continuously adding 3125 parts of methoxy polyether (Mw 2500, formed by polymerization of pure ethylene oxide) into the reaction kettle, heating to 120 ℃ under the negative pressure condition of-0.05 MPa to-0.1 MPa, and stirring for reaction for 5.5 hours; after cooling, the mixture is neutralized by NaOH aqueous solution until PH =7, and water is added to dilute the mixture to 30wt% of water reducing agent solution, so that a reddish brown finished water reducing agent product is obtained, and through GPC test, double peaks appear, the weight average molecular weights are 5621 and 2997 respectively, the molecular weight distributions are 1.09 and 1.05 respectively, and the area ratio of the two peaks is 1:3.
Example 5
(1) Aminolysis reaction
60.1 parts of ethylenediamine and polyethylene glycol dicarboxylic acid derivative diester (R1 in the structural formula I is alkane with 4 carbon atoms, X, Y are both- (CH) 2 CH 2 O) n -H, n = 8) 977.5 parts of the polyamine intermediate containing an amide structure is placed in a reaction kettle, heated to 135 ℃, stirred and reacted for 15 hours, and the polyamine intermediate containing the amide structure is obtained after the reaction is finished.
(2) Phosphorous acidation reaction
And continuously adding 246 parts of phosphorous acid into the reaction kettle, adding 162.4 parts of concentrated hydrochloric acid while stirring, heating to 140 ℃, keeping for 5min, then dropwise adding 243.5 parts of 37wt% formaldehyde water solution, installing a condensing tube, heating and refluxing for 7.5h, and cooling to obtain a phosphrylated polyamine intermediate.
(3) Preparation of water reducing agent
Continuously adding 5175 parts of methoxy polyether (Mw 4500, formed by polymerization of pure ethylene oxide) into the reaction kettle, heating to 100 ℃ under the negative pressure condition of-0.05 MPa to-0.1 MPa, and stirring for reaction for 8 hours; after cooling, the mixture is neutralized by NaOH aqueous solution until the pH is about =7, and water is added to dilute the mixture to 30wt% of water reducing agent solution, so that a reddish brown water reducing agent finished product is obtained, and the weight average molecular weight is 5649 and the molecular weight distribution is 1.10 according to GPC test.
Example 6
(1) Aminolysis reaction
232.4 portions of pentaethylene hexamine and polyethylene glycol dicarboxylic acid derivative monoester (the structural formula IR1 is olefin with 2 carbon atoms, X, Y is respectively H, - (CH) 2 CH 2 O) n -H, n = 6) 570 parts of the polyamine is placed in a reaction kettle, the temperature is raised to 145 ℃, the reaction is stirred for 12.5 hours, and the polyamine intermediate containing the amide structure is obtained after the reaction is finished.
(2) Phosphorous acidation reaction
Adding 574 parts of phosphorous acid into the reaction kettle, adding 232.4 parts of benzenesulfonic acid while stirring, heating to 120 ℃, keeping the temperature for 5min, then dropwise adding 568.1 parts of 37wt% formaldehyde water solution, installing a condensing tube, heating and refluxing for 9h, and cooling to obtain a hypophosphorous polyamine intermediate.
(3) Preparation of water reducing agent
Continuously adding 3000 parts of methoxy polyether (Mw 2000, ethylene oxide and propylene oxide are copolymerized, and the molar ratio of the propylene oxide is 0.10) into the reaction kettle, heating to 85 ℃ under the negative pressure condition of-0.05 MPa to-0.1 MPa, and stirring for reaction for 5 hours. After cooling, the mixture is neutralized by NaOH aqueous solution to PH =7, and is diluted by water to 30wt% of water reducer solution, so that a reddish brown finished water reducer product is obtained, and through GPC test, double peaks appear, the weight average molecular weight is 5061 and 2979 respectively, the molecular weight distribution is 1.08 and 1.05 respectively, and the area ratio of the two peaks is 1:1.
Example 7
(1) Aminolysis reaction
74.1 portions of propane diamine and polyethylene glycol dicarboxylic acid derivative diester (R1 in the structural formula I is alkane with 5 carbon atoms, X, Y are both- (CH) 2 CH 2 O) n -H, n = 9) 1047.2 parts are placed in reactionAnd (3) heating to 150 ℃ in the kettle, stirring and reacting for 6 hours to obtain the polyamine intermediate containing the amide structure after the reaction is finished.
(2) Phosphorous acidation reaction
And continuously adding 246 parts of phosphorous acid into the reaction kettle, adding 74.1 parts of concentrated sulfuric acid while stirring, heating to 100 ℃, keeping for 5min, then dropwise adding 243.5 parts of 37wt% formaldehyde water solution, installing a condensing tube, heating and refluxing for 12.5h, and cooling to obtain a hypophosphorous polyamine intermediate.
(3) Preparation of water reducing agent
1100 parts of methoxy polyether (Mw 1000, formed by polymerization of pure ethylene oxide) is continuously added into the reaction kettle, the temperature is raised to 110 ℃ under the negative pressure condition of-0.05 MPa to-0.1 MPa, and the stirring reaction is carried out for 8.5 hours. After cooling, neutralizing the mixture by using NaOH aqueous solution until the pH is about =7, adding water to dilute the mixture to 30wt% of water reducing agent solution to obtain a reddish brown water reducing agent finished product, and testing by GPC (gel permeation chromatography) that the weight average molecular weight is 1598 and the molecular weight distribution is 1.03.
Example 8
(1) Aminolysis reaction
275 parts of polyethylene polyamine and polyethylene glycol dicarboxylic acid derivative monoester (R1 in the structural formula I is olefin with 4 carbon atoms, X, Y is respectively H, - (CH) 2 CH 2 O) n And (4) -H, n = 4) placing 432 parts of the polyamine into a reaction kettle, heating to 140 ℃, stirring and reacting for 11H to obtain the polyamine intermediate containing the amide structure after the reaction is finished.
(2) Phosphorous acidation reaction
And continuously adding 430.5 parts of phosphorous acid into the reaction kettle, adding 275 parts of methanesulfonic acid while stirring, heating to 135 ℃, keeping for 5min, then dropwise adding 426.1 parts of 37wt% formaldehyde water solution, installing a condensing tube, heating and refluxing for 5h, and cooling to obtain a hypophosphorous polyamine intermediate.
(3) Preparation of water reducing agent
2025 parts of methoxy polyether (Mw 5000, which is formed by copolymerizing ethylene oxide and propylene oxide and the molar ratio of the propylene oxide is 0.02) is continuously added into the reaction kettle, the temperature is increased to 105 ℃ under the negative pressure condition of-0.05 MPa to-0.1 MPa, and the reaction is stirred for 7 hours. After cooling, the mixture is neutralized by NaOH aqueous solution to PH =7, and is diluted by water to 30wt% of water reducing agent solution, so as to obtain a reddish brown water reducing agent finished product, and through GPC test, double peaks appear, the weight average molecular weight is 10994 and 5884 respectively, the molecular weight distribution is 1.13 and 1.07 respectively, and the area ratio of the two peaks is about 6.
Example 9
(1) Aminolysis reaction
114.2 parts of cyclohexanediamine and polyethylene glycol dicarboxylic acid derivative monoester (R1 in the structural formula I is alkane with 5 carbon atoms, X, Y is H, - (CH) respectively 2 CH 2 O) n -H, n = 10) 780 parts of a polyamine intermediate containing an amide structure is placed in a reaction kettle, heated to 130 ℃, stirred and reacted for 7 hours, and the polyamine intermediate containing the amide structure is obtained after the reaction is finished.
(2) Phosphorous acidation reaction
And continuously adding 246 parts of phosphorous acid into the reaction kettle, adding 114.2 parts of trifluoromethanesulfonic acid under stirring, heating to 95 ℃, keeping for 5min, then dropwise adding 426.1 parts of 37wt% formaldehyde aqueous solution, installing a condenser tube, heating and refluxing for 8h, and cooling to obtain a phosphitylated polyamine intermediate.
(3) Preparation of water reducing agent
1950 parts of methoxy polyether (Mw 2500, which is polymerized by pure ethylene oxide) is continuously added into the reaction kettle, the temperature is raised to 120 ℃ under the negative pressure condition of-0.05 MPa to-0.1 MPa, and the reaction is stirred for 9.5 hours. After cooling, the mixture is neutralized by NaOH aqueous solution to PH =7, and is diluted by water to 30wt% of water reducing agent solution, so that a reddish brown finished water reducing agent product is obtained, and through GPC test, double peaks appear, the weight average molecular weights are 4651 and 2525 respectively, the molecular weight distributions are 1.07 and 1.02 respectively, and the area ratio of the two peaks is 3:7.
Example 10
(1) Aminolysis reaction
146.2 parts of triethylene tetramine and polyethylene glycol dicarboxylic acid derivative monoester (R1 in the structural formula I is olefin with 3 carbon atoms, X, Y is respectively H, - (CH) 2 CH 2 O) n And (3) placing 5363 parts of 954.1 in a reaction kettle, heating to 125 ℃, stirring for reaction for 12H, and obtaining the polyamine intermediate containing the amide structure after the reaction is finished.
(2) Phosphorous acidation reaction
And continuously adding 410 parts of phosphorous acid into the reaction kettle, adding 146.2 parts of p-toluenesulfonic acid under stirring, heating to 128 ℃, keeping for 5min, then dropwise adding 405.8 parts of 37wt% formaldehyde aqueous solution, installing a condensing tube, heating and refluxing for 14h, and cooling to obtain a hypophosphorylated polyamine intermediate.
(3) Preparation of water reducing agent
5800 parts of methoxy polyether (Mw 4000, ethylene oxide and propylene oxide are copolymerized, and the molar ratio of propylene oxide is 0.08) are continuously added into the reaction kettle, and the temperature is raised to 115 ℃ under the negative pressure condition of-0.05 MPa to-0.1 MPa, and the stirring reaction is carried out for 8 hours. After cooling, the mixture is neutralized by NaOH aqueous solution to pH =7, and is diluted by water to 30wt% of water reducing agent solution, so as to obtain a reddish brown finished water reducing agent, and through GPC test, double peaks appear, the weight average molecular weight is 8813 and 4717 respectively, the molecular weight distribution is 1.11 and 1.06 respectively, and the area ratio of the two peaks is about 8.
Comparative example 1
(1) Aminolysis reaction
102.2 parts of pentamethylene diamine and polyethylene glycol dicarboxylic acid derivative diester (R1 in the structural formula I is alkane with 2 carbon atoms, X, Y is- (CH) 2 CH 2 O) n And (3) 5363 parts of 611.2 parts of-H, n = 3) are placed in a reaction kettle, the temperature is increased to 148 ℃, the reaction is stirred for 14.5 hours, and after the reaction is finished, a polyamine intermediate containing an amide structure is obtained.
(2) Phosphorous acidation reaction
And continuously adding 246 parts of phosphorous acid into the reaction kettle, adding 3238 parts of concentrated hydrochloric acid zxft 3238 parts under stirring, heating to 80 ℃, keeping for 5min, then dropwise adding 3262 parts of 37% formaldehyde aqueous solution 405.8 parts, installing a condensing tube, heating and refluxing for 12h, and cooling to obtain a hypophosphorylated polyamine intermediate.
(3) Preparation of water reducing agent
2400 parts of methoxy polyether (Mw 1500, formed by polymerizing pure ethylene oxide) is continuously added into the reaction kettle, the temperature is raised to 95 ℃ under the negative pressure condition of-0.05 MPa to-0.1 MPa, and the mixture is stirred and reacted for 10 hours. And (3) cooling, neutralizing with NaOH aqueous solution until the pH is about =7, adding water to dilute to a 30% water reducing agent solution to obtain a reddish brown water reducing agent finished product, wherein the molecular weight is 2922 and the molecular weight distribution is 1.09 through GPC (gel permeation chromatography) test.
Comparative example 2
(1) Aminolysis reaction
189.3 portions of tetraethylenepentamine and polyethylene glycol dicarboxylic acid derivative monoester (R1 in the structural formula I is olefin with 4 carbon atoms, X, Y is respectively H, - (CH) 2 CH 2 O) n And (3) placing 5363 parts of 844.2 in a reaction kettle, heating to 123 ℃, stirring and reacting for 6.5 hours to obtain the polyamine intermediate containing the amide structure after the reaction is finished.
(2) Phosphorous acidation reaction
492 parts of phosphorous acid is continuously added into the reaction kettle, 189.3 parts of benzenesulfonic acid is added under stirring, the temperature is increased to 130 ℃, the reaction kettle is kept for 5min, 487 parts of 37% formaldehyde aqueous solution is dropwise added, a condensing tube is installed, heating reflux is carried out for 6.5h, and cooling is carried out to obtain a phosphrylated polyamine intermediate.
(3) Preparation of water reducing agent
And (2) continuously adding 6300 parts of methoxy polyether (Mw 6000, which is formed by copolymerizing ethylene oxide and propylene oxide and has the mole ratio of the propylene oxide of 0.01) into the reaction kettle, heating to 110 ℃ under the negative pressure condition of-0.05 MPa to-0.1 MPa, and stirring for reacting for 6.5 hours. After cooling, the mixture is neutralized by NaOH aqueous solution until the pH is about =7, and water is added to dilute the mixture to 30% of water reducing agent solution, so that a reddish brown water reducing agent finished product is obtained, and the molecular weight is 7175 and the molecular weight distribution is 1.12 through GPC test.
Comparative example 3
A phosphate-based water reducing agent sample free of carboxylate groups and amide groups was synthesized according to the method described in example 1 of patent CN 108084428A.
Application example 1
Testing the fluidity of the cement paste: referring to GB/T8077-2000, 300g of standard cement and 87g of water are adopted, and detailed data are shown in Table 1.
TABLE 1 neat paste fluidity test
As can be seen from Table 1, the micromolecular phosphate water reducing agent disclosed by the invention not only has better dispersing capacity on cement, but also has better fluidity maintaining capacity. And the cement fluidity of the comparative example is obviously poorer under the same mixing amount.
Application example 2
And (3) testing the setting time, the gas content and the slump: the gas content is determined by referring to a related test method of GB8076-2008 'concrete admixture'; the slump of the fresh concrete of the invention and the change of slump over time of 60min and 120min are determined by referring to a related method of JC473-2001 concrete pumping agent, the mixing amount of the water reducer is fixed to be 0.18 percent of the cement dosage, and the experimental results are shown in Table 2.
TABLE 2 concrete test
The experiment shows that compared with a comparative example, the small molecular phosphate water reducing agent disclosed by the invention can obtain excellent slump retaining capacity under the condition of lower mixing amount. And the concrete slump retaining capacity of the water reducing agent of the comparative example is poorer under the same mixing amount.
Application example 3
To evaluate the sensitivity of the small molecule phosphite water reducer of the present invention to clay, the fluidity of mortar with clay-containing sand configuration was tested. The testing of the expansion degree of the mortar refers to GB/T17671-1999 measuring method of cement mortar fluidity, wherein the used cement is reference cement, the mortar ratio is 1:3; the clay replaces 0.5 percent of the sand by mass; the water-cement ratio was 0.44. The fluidity of the fresh mortar of the invention and the changes of the fluidity over time of 60min and 120min were measured.
TABLE 3 mortar test
The above experiments show that the small molecule phosphate water reducing agent of the present invention has lower sensitivity to clay in sand at lower doping levels than the comparative examples.
Claims (9)
1. A micromolecular phosphate group water reducing agent is characterized in that: the structure of the water reducing agent has phosphite groups, carboxylate groups and amide groups, firstly polyethylene glycol is introduced into a dicarboxylic acid derivative structure, the molecular structure of the water reducing agent takes the dicarboxylic acid derivative as a bridging group, the phosphite groups are introduced as adsorption groups, and finally the water reducing agent is condensed with methoxy polyether to obtain the micromolecule phosphite-based water reducing agent simultaneously containing the carboxylate groups and the amide groups;
the preparation steps of the micromolecule phosphate water reducing agent are as follows:
(1) And (3) aminolysis reaction: carrying out aminolysis reaction on polyamine monomer and polyethylene glycol dicarboxylic acid derivative mono/diester to obtain polyamine intermediate containing an amide structure;
(2) And (3) carrying out a phosphitylation reaction: reacting the polyamine intermediate containing the amide structure with formaldehyde and phosphorous acid to obtain a hypophosphorous polyamine intermediate;
(3) Preparing a micromolecular phosphate group water reducing agent: carrying out condensation reaction on the phosphorylated polyamine intermediate and a methoxy polyether macromonomer to obtain a phosphite micromolecule water reducing agent;
the structure of the polyethylene glycol dicarboxylic acid derivative mono/diester in the step (1) is shown as the formula (I):
wherein R1 is alkane, alkene and derivatives thereof containing 2 to 10 carbon atoms, X, Y is independently selected from H or- (CH) 2 CH 2 O) n -H, and X, Y at least one of which is- (CH) 2 CH 2 O) n -H structure, n is an integer from 3 to 12.
2. The preparation method of the small molecule phosphite water reducing agent as set forth in claim 1, characterized by comprising the following steps:
(1) And (3) aminolysis reaction: carrying out aminolysis reaction on polyamine monomer and polyethylene glycol dicarboxylic acid derivative mono/diester to obtain polyamine intermediate containing an amide structure;
(2) And (3) carrying out a phosphitylation reaction: reacting the polyamine intermediate containing the amide structure with formaldehyde and phosphorous acid to obtain a hypophosphorous polyamine intermediate;
(3) Preparing a micromolecular phosphate group water reducing agent: carrying out condensation reaction on the phosphorylated polyamine intermediate and a methoxy polyether macromonomer to obtain a phosphite micromolecule water reducing agent;
in the step (1), the molar ratio of the polyamine monomer to the polyethylene glycol dicarboxylic acid derivative mono/diester is 1:1.05-1.5;
the molar ratio of the polyamine intermediate containing the amide structure, the phosphorous acid and the formaldehyde in the step (2) is 1 (2m + p) to (2m + p), wherein m and p respectively represent the number of nitrogen atoms of a primary amino group and a secondary amino group in the polyamine intermediate;
the molar ratio of the methoxy polyether macromonomer in the step (3) to the polyethylene glycol dicarboxylic acid derivative mono/diester in the step (1) is 1:1.
3. The method for preparing a small molecular phosphate-based water reducing agent according to claim 2, wherein the polyamine monomer in step (1) is selected from one or more of ethylenediamine, propylenediamine, butylenediamine, pentylenediamine, hexylenediamine, cyclohexanediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, and polyethylenepolyamine.
4. The preparation method of the small molecular phosphite water reducing agent according to claim 3, wherein R1 is selected from alkanes or alkenes containing 2-5 carbon atoms.
5. The preparation method of the small-molecule phosphite water reducing agent according to claim 2, wherein the polyether chain of the methoxy polyether macromonomer is pure ethylene oxide or a mixture of ethylene oxide and propylene oxide; the weight average molecular weight of the methoxy polyether macromonomer is 1000-5000.
6. The preparation method of the small molecule phosphate group water reducing agent according to any one of claims 2 to 5, characterized by comprising the following steps:
(1) Aminolysis reaction: carrying out aminolysis reaction on polyamine monomer and polyethylene glycol dicarboxylic acid derivative mono/diester under certain pressure and temperature conditions to obtain a polyamine intermediate containing an amide structure;
(2) And (3) carrying out a phosphitylation reaction: adding formaldehyde and phosphorous acid into a product obtained in the step (1), and reacting the polyamine intermediate containing the amide structure obtained in the step (1) with formaldehyde and phosphorous acid under a certain condition under the action of a catalyst to obtain a hypophosphorylated polyamine intermediate;
(3) Preparing a micromolecular phosphate group water reducing agent: adding a methoxy polyether macromonomer into the product obtained in the step (2), and carrying out condensation reaction on the hypophosphorylated polyamine intermediate obtained in the step (2) and the methoxy polyether macromonomer under a certain condition to obtain a micromolecule phosphite-based water reducing agent;
the reaction in the step (1) is a solvent-free reaction, the reaction temperature is 120 to 160 ℃, the reaction pressure is the self pressure of a reaction system, and the reaction time is 6 to 15h;
the reaction temperature in the step (2) is 90 to 140 ℃, and the reaction time is 5 to 14h;
the catalyst in the step (2) is a strong acid reagent, and the amount of the catalyst is equal to the mass of the polyamine monomer in the step (1); a condenser reflux device is arranged in the reaction device used in the step (2);
and (3) carrying out reaction at the temperature of 80-120 ℃, for 5-10 h and under the negative pressure condition of-0.05-0.1 MPa.
7. The method for preparing the small molecular phosphate group water reducing agent according to claim 6, wherein the catalyst in the step (2) is selected from any one or more of concentrated hydrochloric acid, concentrated sulfuric acid, methanesulfonic acid, trifluoromethanesulfonic acid, benzenesulfonic acid and p-methanesulfonic acid.
8. The preparation method of the small molecule phosphite water reducing agent according to claim 6, wherein the step (3) further comprises: adding alkali into the micromolecular phosphate water reducing agent for neutralization, and adding water for dilution to a certain concentration to obtain a finished water reducing agent product; the alkali is added for neutralization, naOH aqueous solution with the mass fraction of 30% is used for neutralizing the reaction system to PH =7; and then adding water to dilute the water reducing agent to a mass concentration of 30-50%.
9. The method for applying the small-molecule phosphite water reducing agent of claim 1, wherein the small-molecule phosphite water reducing agent is used as a water dispersant of a hydraulic binder and/or a latent hydraulic binder;
the small molecular phosphate group water reducing agent is used as an additive for cement, lime, gypsum or anhydrous gypsum or a mixture of the components; the latent hydraulic binder is present in the form of a pozzolan, fly ash or blast furnace slag.
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