CN114989412A - Phosphate type polyether monomer and preparation method thereof - Google Patents
Phosphate type polyether monomer and preparation method thereof Download PDFInfo
- Publication number
- CN114989412A CN114989412A CN202210197446.2A CN202210197446A CN114989412A CN 114989412 A CN114989412 A CN 114989412A CN 202210197446 A CN202210197446 A CN 202210197446A CN 114989412 A CN114989412 A CN 114989412A
- Authority
- CN
- China
- Prior art keywords
- phosphate
- polyether
- amine
- polyether monomer
- monomer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229920000570 polyether Polymers 0.000 title claims abstract description 68
- 239000004721 Polyphenylene oxide Substances 0.000 title claims abstract description 66
- 239000000178 monomer Substances 0.000 title claims abstract description 54
- 229910019142 PO4 Inorganic materials 0.000 title claims abstract description 40
- 239000010452 phosphate Substances 0.000 title claims abstract description 40
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 46
- 150000001412 amines Chemical class 0.000 claims abstract description 30
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 28
- 239000004568 cement Substances 0.000 claims abstract description 14
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 14
- 230000026731 phosphorylation Effects 0.000 claims abstract description 13
- 238000006366 phosphorylation reaction Methods 0.000 claims abstract description 13
- 239000002253 acid Substances 0.000 claims abstract description 8
- 239000000126 substance Substances 0.000 claims abstract description 7
- 239000002270 dispersing agent Substances 0.000 claims abstract description 5
- 230000000379 polymerizing effect Effects 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 43
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 30
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 18
- 238000006116 polymerization reaction Methods 0.000 claims description 16
- -1 magnesium aluminum compound Chemical class 0.000 claims description 15
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 14
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- 230000000865 phosphorylative effect Effects 0.000 claims description 9
- 125000002947 alkylene group Chemical group 0.000 claims description 7
- 239000003054 catalyst Substances 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 6
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 6
- 229920002873 Polyethylenimine Polymers 0.000 claims description 6
- 125000005702 oxyalkylene group Chemical group 0.000 claims description 6
- 239000011734 sodium Substances 0.000 claims description 6
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 5
- VHRGRCVQAFMJIZ-UHFFFAOYSA-N cadaverine Chemical compound NCCCCCN VHRGRCVQAFMJIZ-UHFFFAOYSA-N 0.000 claims description 5
- 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 5
- RLOWWWKZYUNIDI-UHFFFAOYSA-N phosphinic chloride Chemical compound ClP=O RLOWWWKZYUNIDI-UHFFFAOYSA-N 0.000 claims description 5
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 claims description 5
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 5
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 125000006353 oxyethylene group Chemical group 0.000 claims description 3
- 229920000642 polymer Polymers 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- MNWBNISUBARLIT-UHFFFAOYSA-N sodium cyanide Chemical compound [Na+].N#[C-] MNWBNISUBARLIT-UHFFFAOYSA-N 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 5
- 238000003786 synthesis reaction Methods 0.000 abstract description 5
- 238000002156 mixing Methods 0.000 abstract description 3
- 239000006185 dispersion Substances 0.000 abstract description 2
- 229920005646 polycarboxylate Polymers 0.000 description 12
- 238000010438 heat treatment Methods 0.000 description 11
- 239000000203 mixture Substances 0.000 description 9
- 238000001816 cooling Methods 0.000 description 8
- 238000007599 discharging Methods 0.000 description 8
- 230000032050 esterification Effects 0.000 description 8
- 238000005886 esterification reaction Methods 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 239000008030 superplasticizer Substances 0.000 description 8
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 7
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 6
- 238000011161 development Methods 0.000 description 6
- 230000018109 developmental process Effects 0.000 description 6
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 description 6
- 230000003472 neutralizing effect Effects 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 238000001514 detection method Methods 0.000 description 4
- 150000005690 diesters Chemical class 0.000 description 4
- 230000007062 hydrolysis Effects 0.000 description 4
- 238000006460 hydrolysis reaction Methods 0.000 description 4
- 239000003999 initiator Substances 0.000 description 4
- 238000005070 sampling Methods 0.000 description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- 230000032683 aging Effects 0.000 description 3
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000012986 chain transfer agent Substances 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 229920000056 polyoxyethylene ether Polymers 0.000 description 3
- 229940051841 polyoxyethylene ether Drugs 0.000 description 3
- 125000001844 prenyl group Chemical group [H]C([*])([H])C([H])=C(C([H])([H])[H])C([H])([H])[H] 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000012086 standard solution Substances 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 150000005215 alkyl ethers Chemical class 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000000691 measurement method Methods 0.000 description 2
- KJFMBFZCATUALV-UHFFFAOYSA-N phenolphthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C(=O)O1 KJFMBFZCATUALV-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- MWRBNPKJOOWZPW-GPADLTIESA-N 1,2-di-[(9E)-octadecenoyl]-sn-glycero-3-phosphoethanolamine Chemical compound CCCCCCCC\C=C\CCCCCCCC(=O)OC[C@H](COP(O)(=O)OCCN)OC(=O)CCCCCCC\C=C\CCCCCCCC MWRBNPKJOOWZPW-GPADLTIESA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 1
- 229960000583 acetic acid Drugs 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- DQYBDCGIPTYXML-UHFFFAOYSA-N ethoxyethane;hydrate Chemical class O.CCOCC DQYBDCGIPTYXML-UHFFFAOYSA-N 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 230000002431 foraging effect Effects 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- CEQFOVLGLXCDCX-WUKNDPDISA-N methyl red Chemical compound C1=CC(N(C)C)=CC=C1\N=N\C1=CC=CC=C1C(O)=O CEQFOVLGLXCDCX-WUKNDPDISA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- DGVVJWXRCWCCOD-UHFFFAOYSA-N naphthalene;hydrate Chemical compound O.C1=CC=CC2=CC=CC=C21 DGVVJWXRCWCCOD-UHFFFAOYSA-N 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- GGHDAUPFEBTORZ-UHFFFAOYSA-N propane-1,1-diamine Chemical compound CCC(N)N GGHDAUPFEBTORZ-UHFFFAOYSA-N 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
- C08G65/321—Polymers modified by chemical after-treatment with inorganic compounds
- C08G65/327—Polymers modified by chemical after-treatment with inorganic compounds containing 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
- 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
- C04B24/246—Phosphorus-containing polymers containing polyether side chains
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
- C08F283/065—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals on to unsaturated polyethers, polyoxymethylenes or polyacetals
-
- C—CHEMISTRY; METALLURGY
- 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
- C08G65/26—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 from cyclic ethers and other compounds
- C08G65/2618—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 from cyclic ethers and other compounds the other compounds containing nitrogen
- C08G65/2621—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 from cyclic ethers and other compounds the other compounds containing nitrogen containing amine groups
- C08G65/2624—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 from cyclic ethers and other compounds the other compounds containing nitrogen containing amine groups containing aliphatic amine groups
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/53—Polyethers
-
- 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
- C04B2103/302—Water reducers
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
- D06M2200/50—Modified hand or grip properties; Softening compositions
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Inorganic Chemistry (AREA)
- Textile Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Polyethers (AREA)
Abstract
The application provides a phosphate type polyether monomer and a preparation method thereof. The novel phosphate type polyether monomer developed by the invention is prepared by reacting amine polyether generated by alkoxylating and polymerizing amine substances with a phosphorylation reagent. Has certain cement dispersant function, certain cement fluidity improving space under the condition of mixing with cement and water, and can also be usedThe water reducer is directly used for synthesis of a polycarboxylic acid water reducer, has special performances of good concrete workability, good dispersion holding capacity, applicability under a low water/ash ratio and the like, and is widely concerned in the industry.
Description
Technical Field
The invention relates to a phosphate type polyether monomer and a preparation method thereof.
Background
At present, polycarboxylic acid high-performance water reducing agents gradually replace naphthalene water reducing agents, and become mainstream products in the market of Chinese concrete water reducing agents. The high-grade concrete is required in the aspects of water conservancy construction, bridges, highways, urban construction and the like, and the polycarboxylate superplasticizer is also an indispensable part of the concrete.
Along with the vigorous popularization of governments, the demand of the polycarboxylate water reducer gradually rises, and is consistent with the rapid development of the polycarboxylate water reducer, and the polycarboxylate water reducer polyether monomer is also rapidly developed. The active monomer for synthesizing the polycarboxylate superplasticizer mainly takes unsaturated esters and unsaturated ethers as main components and mainly contributes to the functional structure of the superplasticizer, and the macromonomer is an important raw material for producing the superplasticizer, so that the market prospect of the macromonomer is generally good along with the development of the water reducer product. Aiming at water reducing agents with different functions, unsaturated ether water reducing agent macromonomer used for synthesis mainly comprises APEG, TPEG, HPEG and EPEG, along with rapid development of the building industry, the market still needs a water reducing agent which has higher water reducing rate, has certain functional functions such as early strength performance, air entraining performance, slump retaining performance and the like, has good slump retaining performance, can reduce pollution as much as possible in the synthesis process and has better workability. Therefore, for researching the synthesis of the functional polycarboxylate superplasticizer, the development of a novel functional polyether monomer is very important.
To meet the market demand, a series of functional polyethers have been developed in succession in various countries, with obvious results in the united states and japan. The main process of technical development is esterification from the end of polyoxyalkylene alkyl ether (PAG) or introduction of silicon and fluorine to develop a series of surface active functional polyethers, which is the main trend of polyether development in recent years. The main varieties with practical value are: a dialkyl polyether (DEPE); ② polyether-polyalkoxyether ester (MEEsPA) by monoether esterification; ③ polyoxyalkene alkyl ether methacrylic acid monoester (PAGMA); fourthly, novel silicon-containing polyether; novel fluoropolyether.
Disclosure of Invention
The invention aims to provide a phosphate type polyether monomer and a preparation method thereof, and the preparation method is simple in process and strong in operability.
The application provides a phosphate type polyether monomer, the structural formula of which is shown as I:
wherein X is structural formula A or B;
R 1 O、R 3 O、R 4 O、R 5 O、R 7 O、R 8 o is one or more of C2-18 oxyalkylene, more than 80% of oxyalkylene is oxyethylene;
a. b, c, d, e, f are integers from 0 to 8, and a + b + c + d + e + f are integers from 1 to 40;
R 2 and R 6 Is an alkylene group having 2 to 10 carbon atoms;
L 1 、L 2 、L 3 、L 4 、L 5 and L 6 Is H or-PO 3 H 2 And L is 1 、L 2 、L 3 、L 4 、L 5 And L 6 Is not H;
t is an integer from 1 to 10;
in one embodiment, the phosphate-based polyether monomer has a weight average molecular weight of 200-1800.
In one embodiment, the phosphate polyether is prepared by reacting amine polyether, which is formed by alkoxylating and polymerizing amine substances, with a phosphorylation agent.
In one embodiment, the amine is any one of ethylenediamine, propylenediamine, butylenediamine, pentylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, polyenepolyamine, and polyethyleneimine.
The present application also provides a method of making the phosphate-based polyether monomer, comprising:
1) carrying out alkoxylation polymerization on amine substances to obtain amino polyether;
2) and reacting the amine polyether with a phosphorylation reagent to obtain the phosphate type polyether monomer.
In one embodiment, the amine is any one of ethylenediamine, propylenediamine, butylenediamine, pentylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, polyenepolyamine, and polyethyleneimine.
In one embodiment, the alkoxylation polymerization reaction temperature is from 110 ℃ to 150 ℃, and the pressure is from 0.3MPa to 0.4 MPa; the catalyst for alkoxylation polymerization is NaOH, KOH, NaCN, Na 2 CO 3 One or more of metallic sodium and metallic magnesium aluminum compound; the amount of the catalyst is 0.05-1.5% of the total amount of the polymer.
In one embodiment, the phosphorylating agent is P 2 O 5 、H 4 P 2 O 7 、POCl 3 One or more of the above; the molar ratio of the amino polyether to the phosphorylation reagent is 1:0.5-2.5, the reaction temperature is 50-100 ℃, and the reaction time is 3-6 hours.
The application also relates to the application of the phosphate ester type polyether monomer as a cement dispersant and the application in the preparation of a polycarboxylic acid water reducing agent.
The novel phosphate type polyether monomer developed by the invention has a certain dispersing property for cement, and can also be directly used for synthesizing a polycarboxylate water reducing agent, and the obtained polycarboxylate water reducing agent has special properties of good concrete workability, good dispersion maintaining capability, applicability at a low water/ash ratio and the like, and is widely concerned in the industry.
Detailed Description
The technical solution of the present invention is further explained below according to specific embodiments. The scope of protection of the invention is not limited to the following examples, which are set forth for illustrative purposes only and are not intended to limit the invention in any way.
The application provides a phosphate type polyether monomer, the structural formula of which is shown as I:
wherein X is structural formula A or B;
R 1 O、R 3 O、R 4 O、R 5 O、R 7 O、R 8 o is one or more of C2-18 oxyalkylene, more than 80% of oxyalkylene is oxyethylene;
a. b, c, d, e, f are integers from 0 to 8, and a + b + c + d + e + f are integers from 1 to 40;
R 2 and R 6 Is an alkylene group having 2 to 10 carbon atoms;
L 1 、L 2 、L 3 、L 4 、L 5 and L 6 Is H or-PO 3 H 2 And L is 1 、L 2 、L 3 、L 4 、L 5 And L 6 Is not H;
t is an integer from 1 to 10;
the monomer I can be obtained as follows: the preparation method is characterized in that amine substances are subjected to alkoxylation polymerization to produce amine polyether, and then the amine polyether reacts with a phosphorylation reagent to obtain the product.
In one embodiment, the amine may be any one of ethylenediamine, propylenediamine, butylenediamine, pentylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, polyenepolyamine, and polyethyleneimine. In one embodiment, the alkoxylated species used in the alkoxylation polymerization reaction may include one or more of ethylene oxide, propylene oxide, butylene oxide, epoxy resins, epichlorohydrin, and the like.
In one embodiment, the alkoxylation polymerization reaction temperature may range from 110 ℃ to 150 ℃ and a pressure of 0.3MPa to 0.4 MPa. In one embodiment, the alkoxylated polymerization catalyst is NaOH, KOH, NaCN, Na 2 CO 3 One or more of metallic sodium and metallic magnesium aluminum compound. In one embodiment, the catalyst is used in an amount of 0.05 to 1.5% of the total polymer.
In one embodiment, the phosphorylating agent is P 2 O 5 、H 4 P 2 O 7 、POCl 3 One or more of the above; the molar ratio of the amino polyether to the phosphorylation reagent is 1:0.5-2.5, the reaction temperature is 50-100 ℃, and the reaction time is 3-6 hours.
The alkoxylation polymerization can be carried out as follows, specifically comprising the steps of:
(1) adding a certain amount of amine substances into a reaction kettle, adding a catalyst accounting for 0.05-1.5% of the total amount, and introducing N 2 After the replacement is qualified, the temperature of the reaction kettle is raised, and the stirrer is started at the same time.
(2) Controlling the reaction pressure to be less than 0.4MPa, controlling the reaction temperature to be 110-150 ℃, introducing alkylene oxide (such as ethylene oxide), adding the rest alkylene oxide (such as propylene oxide) after the alkylene oxide (such as ethylene oxide) is completely added, keeping the kettle temperature at 110-150 ℃ for polymerization reaction, and keeping the temperature for aging after the rest alkylene oxide (such as propylene oxide) is completely added. And then cooling, neutralizing with glacial acetic acid until the pH value is 6-7, and discharging to obtain the amino polyether.
(3) Product index measurements were carried out with reference to the amine number measurement in DIN 16945.
Then, the resulting amino polyether is reacted with a phosphorylating agent to obtain the monomer I. In one embodiment, the phosphorylating agent may be P 2 O 5 、H 4 P 2 O 7 、POCl 3 One or more of them. And (3) reacting the amine polyether with a phosphorylation reagent to obtain the polyether with phosphate ester at the tail end. The adding speed of the phosphating reagent in the reaction process is controlled, the speed is too high, the reaction is violent and insufficient, and parts are easy to appearA coke-like substance; the addition of the phosphorylating agent is strictly controlled over a defined period of time. In one embodiment, the molar ratio of the amine-based polyether to the phosphorylating agent may be 1:0.5-2.5, the reaction temperature is 50-100 ℃, and the reaction time is 3-6 hours.
For each group in the monomer I, it can also be determined with reference to the preparation as follows:
1) the choice of X, A or B, in formula I can be determined by the initiator.
2) The values of a, b, c, d, e, f can be determined according to the addition number of ethylene oxide and propylene oxide; it can also be determined from the amine value, for example, when the amine value is 0, it means that a, b, c, d, e, and f are all 1.
3) The amount of phosphate can be determined according to the molar ratio of the reaction of the phosphating reagent and the amine polyether monomer in the reaction process. For example, when the phosphorylating agent is in excess, the structural termini are capped with phosphate.
Thus, a phosphate type polyether monomer of the present application was obtained, which had the following properties: the weight average molecular weight is 200-1800.
The phosphate type polyether monomer has a certain cement dispersing function, has a certain effect of improving the fluidity of cement under the condition of mixing with cement and water, and can be directly used as a cement dispersing agent; can also be used as a raw material for preparing the polycarboxylic acid water reducing agent.
The measurement method of the phosphate ester component and the measurement method of the esterification rate are given below:
determination of the phosphate ester component in the product: accurately weighing 1-2 g of sample in a 250mL conical flask, adding 50mL of absolute ethyl alcohol, fully oscillating to dissolve the sample, dropwise adding 2-3 drops of methyl red indicator, titrating with 0.5mol/L potassium hydroxide standard solution to change the solution from red to orange yellow, and recording the volume V of the consumed potassium hydroxide standard solution 1 . Dripping 6-8 drops of phenolphthalein indicator, continuing to titrate, changing the solution from yellow to orange red, and recording the volume V of the consumed potassium hydroxide standard solution 2 . 10mL of 10% aqueous calcium chloride solution were added and the titration continued, the solution changing from red to orange-yellow, and the volume V of the standard potassium hydroxide solution consumed was recorded 3 . The calculation formula is shown as follows:
the acid values were determined at different reaction time points. The esterification rate was calculated by comparison with the initial acid value.
The following abbreviations are used in the examples:
Ⅰ-1：R 1 O、R 3 O、R 4 O、R 5 o is-CH 2 CH 2 O-，t＝1，a＝b＝c＝d＝1，R 2 is-CH 2 CH 2 -, X are of the formulae A, L 1 、L 2 、L 3 、L 4 is-PO 3 H 2
Ⅰ-2：R 1 O、R 3 O、R 4 O、R 5 O is-CH (CH) 3 )CH 2 O-，t＝1，a＝b＝c＝d＝1，R 2 is-CH 2 CH 2 CH 2 CH 2 -, X are of the formulae A, L 1 、L 2 、L 3 、L 4 is-PO 3 H 2
Ⅰ-3：R 1 O、R 3 O、R 4 O、R 5 O is-CH 2 CH 2 O-，t＝2，a＝b＝c＝d＝1，R 2 is-CH 2 CH 2 -, X are of the formulae A, L 1 、L 2 、L 3 、L 4 is-PO 3 H 2
Ⅰ-4：R 1 O、R 3 O、R 4 O、R 7 O、R 8 O is-CH 2 CH 2 O-，t＝10，a＝b＝c＝e＝f＝1，R 2 is-CH 2 CH 2 ，R 6 is-CH 2 CH 2 X is structural formula B, L 1 、L 2 、L 3 is-PO 3 H 2 ，L 5 、L 6 Is H
Example 1
Firstly, 1mol of ethylene diamine monomer is pumped into a reaction kettle, and N is used 2 Heating the reaction kettle after replacement, introducing 4mol of ethylene oxide into the reaction kettle when the temperature of the reaction kettle is raised to 90 ℃, controlling the reaction temperature within the range of 120-130 ℃ to carry out curing reaction for 30min, and then discharging when the pressure drop of the reaction kettle is zero to obtain the amino polyether monomer. 1mol of amino polyether monomer is added into a three-neck flask provided with a thermometer and a stirrer, the stirring is started, and a phosphorylation reagent POCl is slowly added in batches 3 1.5mol (not more than 40 ℃), slowly heating to 70 ℃, keeping the temperature, continuously reacting for 3 hours, adding water for hydrolysis, sampling and measuring the amount of monoester and diester phosphate in the product, then cooling to below 50 ℃, neutralizing with a sodium hydroxide solution until the pH value is 6-8, and obtaining the phosphorylated polyether product I-1.
TABLE 1 detection index for phosphorylated polyether monomers
| Number of | Amine number/meq/g | Content of monoester/%) | Content of diester/%) | Degree of esterification/%) |
| I-1 | 0 | 80.2 | 12.7 | 88 |
Example 2
Firstly, 1mol of monomer propane diamine is pumped into a reaction kettle, and N is used 2 Heating the reaction kettle after replacement, introducing 4mol of propylene oxide into the reaction kettle when the temperature of the reaction kettle is raised to 90 ℃, controlling the temperature in the kettle to be 120 ℃, carrying out polymerization reaction for 120min, carrying out curing reaction for 30min after the polymerization reaction is finished, and then discharging when the pressure drop of the kettle is zero to obtain the amino polyether monomer. 1.5mol of amino polyether monomer is added into a three-neck flask provided with a thermometer and a stirrer, the stirring is started, and the phosphorylation reagent P is slowly added in batches 2 O 5 2mol (not more than 40 ℃), slowly heating to 70 ℃, keeping the temperature and continuously reacting for 3 hours after adding, adding water for hydrolysis, sampling and measuring the amount of monoester and diester phosphate in the product, then cooling to below 50 ℃, and neutralizing with sodium hydroxide solution until the pH value is 6-8 to prepare a phosphorylated polyether product I-2.
TABLE 2 detection of phosphorylated polyether monomers
| Numbering | Amine number/meq/g | Content of monoester/%) | Content of diester/%) | Degree of esterification/%) |
| I-2 | 0 | 81.5 | 14.7 | 89 |
Example 3
Firstly, 1mol of monomer diethylenetriamine is introduced into a reaction kettle, and N is used 2 Heating the reaction kettle after replacement, introducing propylene oxide into the reaction kettle when the temperature of the reaction kettle is raised to 90 ℃, and carrying out polymerization reaction for 120min when 4mol of propylene oxide is completely introduced into the reaction kettle. And (3) after the polymerization reaction is finished, carrying out curing reaction for 30min, and then discharging when the pressure drop of the kettle is zero to obtain the amino polyether monomer. 1mol of amino polyether monomer is added into a three-neck flask provided with a thermometer and a stirrer, the stirring is started, and the phosphorylation reagent P is slowly added in batches 2 O 5 2.5mol (not more than 40 ℃), slowly heating to 70 ℃, keeping the temperature, continuously reacting for 3 hours after adding, adding water for hydrolysis, sampling and measuring the amount of monoester and diester phosphate in the product, cooling to below 50 ℃, and neutralizing with sodium hydroxide solution until the pH value is 6-8 to obtain the phosphorylated polyether product I-3.
TABLE 3 detection of phosphorylated polyether monomers
| Numbering | Amine number/meq/g | Content of monoester/%) | Content of diester/%) | Degree of esterification/%) |
| I-3 | 0 | 84.9 | 10.2 | 90 |
Example 4
Firstly, 1mol of monomer polyethyleneimine is fed into a reaction kettle, a catalyst metal magnesium aluminum compound with the total amount of 0.2 percent is added, and N is used 2 Heating the reaction kettle after replacement, introducing ethylene oxide into the reaction kettle when the temperature of the reaction kettle is raised to 90 ℃, and carrying out polymerization reaction for 120min when 5mol of ethylene oxide is completely introduced into the reaction kettle. Then curing reaction is carried out for 30min at the reaction temperature of 115-120 ℃, and then discharging is carried out when the pressure drop of the kettle is zero, thus obtaining the amino polyether monomer. 1mol of amino polyether monomer is added into a three-neck flask provided with a thermometer and a stirrer, the stirring is started, and a phosphorylation reagent H is slowly added in batches 4 P 2 O 7 1.5mol (not more than 40 ℃), slowly heating to 70 ℃, keeping the temperature, continuously reacting for 3 hours after adding, adding water for hydrolysis, sampling and measuring the amount of monoester and diester phosphate in the product, cooling to below 50 ℃, and neutralizing with sodium hydroxide solution until the pH value is 6-8 to obtain a phosphorylated polyether product I-4.
TABLE 4 detection indices of phosphorylated polyether monomers
| Numbering | Amine number/meq/g | Content of monoester/%) | Content of diester/%) | Degree of esterification/%) |
| I-4 | 0 | 81.8 | 15.3 | 91 |
Water reducing agent application example 1
Adding 120.0g of deionized water into a 500ml four-neck flask provided with a stirrer, a thermometer and a dropping device, stirring and heating to 60 ℃, adding 124 g of prenyl polyoxyethylene ether and 60 g of acrylic acid, adding 10 g of I-3 (example 3) after the monomers are dissolved, dropping an initiator (a mixture of 5 g of ammonium persulfate and 25 g of water) and a chain transfer agent (a mixture of 1 g of thioglycolic acid and 40 g of water) for 3 hours at a constant speed, aging for 2 hours, cooling the system temperature to normal temperature after the reaction is finished, adjusting the pH value of the mixture obtained by the reaction to be neutral by using a NaOH aqueous solution with the mass concentration of 30%, and discharging to obtain a high-performance polycarboxylate superplasticizer product YA-1 with the solid content of 40%.
Water reducing agent application example 2
Adding 120.0g of deionized water into a 500ml four-neck flask provided with a stirrer, a thermometer and a dropping device, stirring and heating to 60 ℃, adding 124 g of prenyl polyoxyethylene ether and 60 g of acrylic acid, adding 10 g of I-2 (example 2) after the monomers are dissolved, dropping an initiator (5 g of ammonium persulfate and 25 g of water mixture) and a chain transfer agent (1 g of mercaptoacetic acid and 40 g of water mixture) for 3 hours at a constant speed, aging for 2 hours, cooling the system temperature to normal temperature after the reaction is finished, adjusting the pH value of the mixture obtained by the reaction to be neutral by using a NaOH aqueous solution with the mass concentration of 30%, discharging, and obtaining a high-performance polycarboxylate superplasticizer product YA-2, wherein the solid content of the obtained product is 40%.
Water reducing agent application comparative example 1
Adding 120.0g of deionized water into a 500ml four-neck flask provided with a stirrer, a thermometer and a dropping device, stirring and heating to 60 ℃, adding 134 g of prenyl polyoxyethylene ether and 60 g of acrylic acid, then dropping an initiator (a mixture of 5 g of ammonium persulfate and 25 g of water) and a chain transfer agent (a mixture of 1 g of mercaptoacetic acid and 40 g of water), respectively dropping at a constant speed for 3 hours, wherein the aging time is 2 hours, cooling the system to normal temperature after the reaction is finished, adjusting the pH value of the mixture obtained by the reaction to be neutral by using a NaOH aqueous solution with the mass concentration of 30%, and discharging to obtain a high-performance polycarboxylic acid water reducer product DA-1, wherein the solid content of the product is 40%.
The water reducing agents synthesized in the application examples 1 and 2 and the application comparative example 1 were designed in accordance with JGJ55 with reference to a certain mixing ratio with cement, sand, gravel, water, and other additives. The temperature of various concrete test materials and the environment is kept at (20 +/-3) DEG C; please refer to GB/8076-.
TABLE 5 evaluation data of concrete containing phosphate type polycarboxylate superplasticizer
As can be seen from the concrete evaluation data of the phosphate-containing polycarboxylate water reducer in Table 5, the water reducer of the application example of the present invention has equivalent performance to the water reducer of the application comparative example 1, but the backflow time of the YA-1 water reducer is 4s faster than that of the water reducer of the comparative example DA-1, which indicates that the addition of I-1, I-2, I-3 and I-4 in the examples during the synthesis of the water reducer has a certain effect of improving the backflow time of concrete.
Net paste Performance test
The above obtained phosphorylated polyether products I-1 to I-4 were tested for neat paste properties according to the homogeneity test method for the concrete admixture of GB/T8077-2012, and the results are shown in table 6.
TABLE 6 Net paste Performance test of phosphate type monomers
As can be seen from the data of the neat paste performance test of the phosphate ester type monomer shown in Table 6, the addition of the monomer I in the embodiment of the invention is compared with the cement fluidity without the addition of the monomer I, and the fluidity value is increased to a certain extent, which indicates that the phosphate ester type monomer has a certain promotion space for the fluidity of cement paste and can be directly used as a cement dispersant.
It should be noted by those skilled in the art that the described embodiments of the present invention are merely exemplary and that various other substitutions, alterations, and modifications may be made within the scope of the present invention. Accordingly, the present invention is not limited to the above-described embodiments, but is only limited by the claims.
Claims (10)
1. A phosphate type polyether monomer is shown as a structural formula I:
wherein X is structural formula A or B;
R 1 O、R 3 O、R 4 O、R 5 O、R 7 O、R 8 o is one or more of C2-18 oxyalkylene, more than 80% of oxyalkylene is oxyethylene;
a. b, c, d, e, f are integers from 0 to 8, and a + b + c + d + e + f are integers from 1 to 40;
R 2 and R 6 Is alkylene having 2 to 10 carbon atoms;
L 1 、L 2 、L 3 、L 4 、L 5 and L 6 Is H or-PO 3 H 2 And L is 1 、L 2 、L 3 、L 4 、L 5 And L 6 Is not H;
t is an integer from 1 to 10.
2. The phosphate-based polyether monomer according to claim 1, wherein the weight average molecular weight of the phosphate-based polyether monomer is 200-1800.
3. The phosphate polyether monomer according to claim 1, wherein the phosphate polyether is prepared by reacting an amine polyether, which is obtained by alkoxylating and polymerizing an amine, with a phosphorylating agent.
4. The phosphate polyether monomer according to claim 3, wherein the amine is any one of ethylenediamine, propylenediamine, butylenediamine, pentylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, polyenepolyamine, and polyethyleneimine.
5. A method of preparing the phosphate-based polyether monomer of any one of claims 1-4, comprising:
1) carrying out alkoxylation polymerization on amine substances to obtain amino polyether;
2) and reacting the amine polyether with a phosphorylation reagent to obtain the phosphate type polyether monomer.
6. The method according to claim 5, wherein the amine is any one of ethylenediamine, propylenediamine, butylenediamine, pentylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, polyenepolyamine, and polyethyleneimine.
7. The process of claim 5, wherein the alkoxylation polymerization reaction temperature is 110 ℃ to 150 ℃, and the pressure is 0.3MPa to 0.4 MPa; the catalyst for alkoxylation polymerization is NaOH, KOH, NaCN, Na 2 CO 3 One or more of metallic sodium and metallic magnesium aluminum compound; the amount of the catalyst is 0.05-1.5% of the total amount of the polymer.
8. The method of claim 5, wherein the phosphorylating agent is P 2 O 5 、H 4 P 2 O 7 、POCl 3 One or more of the above; the molar ratio of the amine polyether to the phosphorylation reagent is 1:0.5-2.5, the reaction temperature is 50-100 ℃, and the reaction time is 3-6 hours.
9. Use of the phosphate-based polyether monomer according to any one of claims 1 to 4 as a cement dispersant.
10. Use of the phosphate-based polyether monomer according to any one of claims 1-4 in the preparation of a polycarboxylic acid water reducer.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110231117 | 2021-03-02 | ||
| CN2021102311170 | 2021-03-02 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN114989412A true CN114989412A (en) | 2022-09-02 |
Family
ID=83023650
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210197446.2A Pending CN114989412A (en) | 2021-03-02 | 2022-03-01 | Phosphate type polyether monomer and preparation method thereof |
| CN202210197438.8A Pending CN114989411A (en) | 2021-03-02 | 2022-03-01 | Unsaturated phosphate type polyether monomer and preparation method thereof |
Family Applications After (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210197438.8A Pending CN114989411A (en) | 2021-03-02 | 2022-03-01 | Unsaturated phosphate type polyether monomer and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (2) | CN114989412A (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107987271A (en) * | 2017-12-11 | 2018-05-04 | 江苏苏博特新材料股份有限公司 | A kind of preparation method of phosphoric acid ester group low molecule water-reducing agent |
| CN108250429A (en) * | 2016-12-28 | 2018-07-06 | 江苏苏博特新材料股份有限公司 | The anti-stick soil type phosphate super plasticizer of low relative molecular weight, preparation method and the usage |
| WO2021027174A1 (en) * | 2019-08-14 | 2021-02-18 | 科之杰新材料集团有限公司 | Water-retaining type polycarboxylate superplasticizer and preparation method therefor |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104261721B (en) * | 2014-09-22 | 2016-06-29 | 科之杰新材料集团有限公司 | A kind of ethers polycarboxylic acid slump retaining agent and preparation method thereof |
| CN106317402A (en) * | 2016-08-19 | 2017-01-11 | 浙江皇马科技股份有限公司 | Polyether monomer and preparation method and application thereof |
-
2022
- 2022-03-01 CN CN202210197446.2A patent/CN114989412A/en active Pending
- 2022-03-01 CN CN202210197438.8A patent/CN114989411A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108250429A (en) * | 2016-12-28 | 2018-07-06 | 江苏苏博特新材料股份有限公司 | The anti-stick soil type phosphate super plasticizer of low relative molecular weight, preparation method and the usage |
| CN107987271A (en) * | 2017-12-11 | 2018-05-04 | 江苏苏博特新材料股份有限公司 | A kind of preparation method of phosphoric acid ester group low molecule water-reducing agent |
| WO2021027174A1 (en) * | 2019-08-14 | 2021-02-18 | 科之杰新材料集团有限公司 | Water-retaining type polycarboxylate superplasticizer and preparation method therefor |
Non-Patent Citations (1)
| Title |
|---|
| 郭延辉等主编: "《聚羧酸系高性能减水剂研究与工程应用》", 30 June 2007, 中国铁道出版社, pages: 122 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114989411A (en) | 2022-09-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US10647803B2 (en) | Method for preparing concrete superplasticizer having phosphorous acid group and use thereof | |
| EP3398916B1 (en) | Phosphorylated polycondensate as high efficiency water reducing agent and preparation method thereof | |
| KR100615378B1 (en) | Polycarboxylic acid type copolymer and method for producing the same, and use of the same | |
| JP4883757B2 (en) | AE concrete manufacturing method and AE concrete | |
| CN108250448B (en) | Preparation method and application of low-molecular concrete water reducing agent containing phosphoric acid group | |
| CN111378113A (en) | Phosphated polyether, preparation method thereof and application thereof in preparation of high-adaptability phosphonic acid-based water reducing agent | |
| JP2003300766A (en) | Concrete composition, method for producing the same and cement admixture | |
| US9777133B2 (en) | Additive for hydraulically setting compounds | |
| JP2003128738A (en) | Polycarboxylic acid-based copolymer, method for producing the same and application of the same | |
| CN108264620B (en) | Phosphonic acid group block polymer, preparation method and application thereof | |
| US8536252B2 (en) | Semi continuously operated method for producing copolymers | |
| CN108059718B (en) | Preparation method of cement dispersant with clay adaptability and viscosity reduction effect | |
| CN107337788B (en) | Special multi-element phosphate additive for medium-low slump concrete and preparation method thereof | |
| CN114989412A (en) | Phosphate type polyether monomer and preparation method thereof | |
| CN107382129B (en) | Polycarboxylate superplasticizer, preparation method thereof and cement admixture | |
| JP7107613B2 (en) | Additive for hydraulic composition | |
| JP5467859B2 (en) | Method for producing cement dispersant | |
| JP2004137130A (en) | Additive composition for cement | |
| CN111378111B (en) | Phosphonate water reducing agent without halogen ions, and preparation method and application thereof | |
| CN114989367B (en) | Phosphate type polycarboxylic acid copolymer, preparation method thereof and polycarboxylic acid water reducer | |
| CN114133492A (en) | Preparation method of polycarboxylic acid concrete water reducing agent | |
| CN111378117B (en) | Low-molecular-weight phosphate water reducing agent and preparation method and application thereof | |
| JP4974771B2 (en) | Polycarboxylic acid copolymer, method for producing the same, and use thereof | |
| CN109970894B (en) | Polymer type concrete defoaming agent, preparation method and application thereof | |
| US20120095134A1 (en) | Viscosity-reducing super-plasticising copolymers |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |