CN114685296A - Preparation method of polyether intermediate containing aldehyde group and amino group and application of polyether intermediate in phosphate water reducing agent - Google Patents
Preparation method of polyether intermediate containing aldehyde group and amino group and application of polyether intermediate in phosphate water reducing agent Download PDFInfo
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 115
- 239000003638 chemical reducing agent Substances 0.000 title claims abstract description 73
- 239000004721 Polyphenylene oxide Substances 0.000 title claims abstract description 52
- 229920000570 polyether Polymers 0.000 title claims abstract description 52
- 125000003172 aldehyde group Chemical group 0.000 title claims abstract description 47
- 125000003277 amino group Chemical group 0.000 title claims abstract description 47
- 229910019142 PO4 Inorganic materials 0.000 title claims abstract description 22
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 title claims abstract description 22
- 239000010452 phosphate Substances 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000000178 monomer Substances 0.000 claims abstract description 56
- 229920000768 polyamine Polymers 0.000 claims abstract description 27
- 238000006845 Michael addition reaction Methods 0.000 claims abstract description 9
- 238000006467 substitution reaction Methods 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims description 107
- 150000001299 aldehydes Chemical class 0.000 claims description 30
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 claims description 26
- 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 claims description 23
- 239000003054 catalyst Substances 0.000 claims description 21
- 239000000126 substance Substances 0.000 claims description 17
- 238000001816 cooling Methods 0.000 claims description 16
- 238000001914 filtration Methods 0.000 claims description 16
- 230000003472 neutralizing effect Effects 0.000 claims description 16
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- STNJBCKSHOAVAJ-UHFFFAOYSA-N Methacrolein Chemical compound CC(=C)C=O STNJBCKSHOAVAJ-UHFFFAOYSA-N 0.000 claims description 11
- MLUCVPSAIODCQM-NSCUHMNNSA-N crotonaldehyde Chemical compound C\C=C\C=O MLUCVPSAIODCQM-NSCUHMNNSA-N 0.000 claims description 11
- MLUCVPSAIODCQM-UHFFFAOYSA-N crotonaldehyde Natural products CC=CC=O MLUCVPSAIODCQM-UHFFFAOYSA-N 0.000 claims description 11
- YZUPZGFPHUVJKC-UHFFFAOYSA-N 1-bromo-2-methoxyethane Chemical compound COCCBr YZUPZGFPHUVJKC-UHFFFAOYSA-N 0.000 claims description 8
- 238000006683 Mannich reaction Methods 0.000 claims description 8
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 8
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 8
- 230000035484 reaction time Effects 0.000 claims description 7
- VHRGRCVQAFMJIZ-UHFFFAOYSA-N cadaverine Chemical compound NCCCCCN VHRGRCVQAFMJIZ-UHFFFAOYSA-N 0.000 claims description 6
- SEPQTYODOKLVSB-UHFFFAOYSA-N 3-methylbut-2-enal Chemical compound CC(C)=CC=O SEPQTYODOKLVSB-UHFFFAOYSA-N 0.000 claims description 4
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 4
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 4
- ACWQBUSCFPJUPN-UHFFFAOYSA-N Tiglaldehyde Natural products CC=C(C)C=O ACWQBUSCFPJUPN-UHFFFAOYSA-N 0.000 claims description 4
- 230000009471 action Effects 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
- 229940098779 methanesulfonic acid Drugs 0.000 claims description 4
- 230000026731 phosphorylation Effects 0.000 claims description 4
- 238000006366 phosphorylation reaction Methods 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-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
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims description 3
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 3
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 3
- 230000015572 biosynthetic process Effects 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
- 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
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 3
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 claims description 3
- 238000003786 synthesis reaction Methods 0.000 claims description 3
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 claims description 3
- XGSZRMLYTKMPFE-UHFFFAOYSA-N 2,3-dimethylbut-2-enal Chemical compound CC(C)=C(C)C=O XGSZRMLYTKMPFE-UHFFFAOYSA-N 0.000 claims description 2
- 229930040373 Paraformaldehyde Natural products 0.000 claims description 2
- 239000003377 acid catalyst Substances 0.000 claims description 2
- 150000001768 cations Chemical class 0.000 claims description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 230000001939 inductive effect Effects 0.000 claims description 2
- 238000010907 mechanical stirring Methods 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 229920002866 paraformaldehyde Polymers 0.000 claims description 2
- 230000008569 process Effects 0.000 claims description 2
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 claims description 2
- 239000011347 resin Substances 0.000 claims description 2
- 229920005989 resin Polymers 0.000 claims description 2
- 238000007142 ring opening reaction Methods 0.000 claims description 2
- 238000006561 solvent free reaction Methods 0.000 claims description 2
- ACWQBUSCFPJUPN-HWKANZROSA-N trans-2-methyl-2-butenal Chemical compound C\C=C(/C)C=O ACWQBUSCFPJUPN-HWKANZROSA-N 0.000 claims description 2
- 238000007738 vacuum evaporation Methods 0.000 claims 1
- 239000004927 clay Substances 0.000 abstract description 10
- 230000001603 reducing effect Effects 0.000 abstract description 6
- 230000000979 retarding effect Effects 0.000 abstract description 4
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 abstract description 2
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 abstract 3
- 238000003756 stirring Methods 0.000 description 43
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 42
- 238000010438 heat treatment Methods 0.000 description 37
- 238000005227 gel permeation chromatography Methods 0.000 description 31
- 238000012360 testing method Methods 0.000 description 22
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 17
- 239000000243 solution Substances 0.000 description 15
- 239000004568 cement Substances 0.000 description 14
- 238000009826 distribution Methods 0.000 description 14
- 239000008098 formaldehyde solution Substances 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 13
- 238000001704 evaporation Methods 0.000 description 7
- 239000004570 mortar (masonry) Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 238000002156 mixing Methods 0.000 description 5
- 239000004576 sand Substances 0.000 description 5
- 238000011160 research Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 3
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- QVYARBLCAHCSFJ-UHFFFAOYSA-N butane-1,1-diamine Chemical compound CCCC(N)N QVYARBLCAHCSFJ-UHFFFAOYSA-N 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000005086 pumping Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 2
- 239000008030 superplasticizer Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 229960001124 trientine Drugs 0.000 description 2
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 229920002873 Polyethylenimine Polymers 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 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
- 238000010276 construction Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000005357 flat glass Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 230000014759 maintenance of location Effects 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
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical group OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 229920005646 polycarboxylate Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C221/00—Preparation of compounds containing amino groups and doubly-bound oxygen atoms bound to the same carbon skeleton
-
- 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
- C04B24/28—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C04B24/30—Condensation polymers of aldehydes or ketones
-
- 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
- C08G12/00—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
- C08G12/02—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes
- C08G12/04—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with acyclic or carbocyclic compounds
- C08G12/06—Amines
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/14—The ring being saturated
Abstract
The invention discloses a preparation method of a polyether intermediate containing aldehyde groups and amino groups and application of the polyether intermediate in a phosphate water reducing agent. The preparation method of the intermediate containing aldehyde group and amino group is obtained by carrying out Michael addition reaction on a polyamine monomer and an unsaturated aldehyde monomer, wherein the molar ratio of the polyamine monomer to the unsaturated aldehyde monomer is 1: 1.5-2. The intermediate containing aldehyde group and amino group and chlorinated polyether are subjected to substitution reaction to obtain a polyether macromonomer containing aldehyde group and amino group; the polyether macromonomer containing aldehyde group and amino group is used for preparing the phosphate water reducing agent. According to the preparation method of the phosphate water reducing agent, a basic reticular framework is formed by utilizing the property of a polyfunctional group of an unsaturated aldehyde monomer and amino polyether, and the obtained phosphate water reducing agent is a body type polymeric water reducing agent which has excellent water reducing performance, and is more excellent in slump retaining, retarding and clay tolerance performance.
Description
Technical Field
The invention belongs to the field of preparation of concrete admixtures, and particularly relates to a polyether intermediate containing aldehyde groups and amino groups, a preparation method of the polyether intermediate and application of the polyether intermediate in a phosphate water reducing agent.
Background
The water reducing agent is an important component in modern concrete, can regulate and control the rheological property of the concrete, improve the mechanical property, improve the durability and the like, and provides a premise and guarantee for the development of the concrete towards high performance.
In recent years, polycarboxylic acid water reducing agents have become mainstream researches in the industry due to the advantages of low mixing amount, high water reducing rate, good cement adaptability and the like. However, with the rapid development of Chinese economy, various targeted requirements in the building industry are increasingly appearing, and more new requirements are also put forward on the cement water reducing agent technology. 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, shrinkage increase, easy cracking and the like. Polycarboxylic acid water reducing agents also gradually show a phenomenon that is difficult to satisfy in the presence of such diversified demands.
In order to solve the urgent problem in the water reducing agent industry, engineering technicians and researchers introduce phosphate groups with high adsorbability from the level of the molecular construction of the water reducing agent based on the research theory. On one hand, the added phosphate group has stronger charge attraction than the carboxyl group; on the other hand, the added phosphate group can improve the tolerance of the water reducing agent to calcium ions in a cement paste system. At present, various patents and documents disclose methods for preparing phosphate-based water reducing agents and the effects obtained.
Patent document CN102439063B discloses a low molecular weight phosphoric acid water reducing agent. The water reducing agent shows a certain retardation effect, and the retardation effect can be prolonged along with the increase of the mixing amount. The water reducing agent has high preparation cost and difficult application.
Patent document CN103342500A reports a clay shielding agent compounded from phosphate and other raw materials, and the water reducing agent can be preferentially adsorbed on the surface of clay particles in sandstone aggregates, thereby ensuring the effect of the polycarboxylic acid water reducing agent.
Patent document CN103596993A discloses a copolymer with gem-bisphosphonate groups, which is less sensitive to clays than polycarboxylic acid water reducing agents.
Patent document CN105504297A reports a phosphorous acid concrete superplasticizer with a polyethyleneimine structure. The polyether derivative can be used alone or in combination with sulfonate water reducers, polycarboxylic acid water reducers and the like, and can effectively improve the flowing property and slump retaining property of concrete.
The above patent articles and the like disclose different types of phosphate-based water reducing agents exhibiting remarkable slump retaining, set retarding and water reducing properties and a certain clay resistance without losing other properties such as strength of concrete. The performance of the phosphate water reducing agent is gradually paid attention and accepted by workers in the industry, but compared with the polycarboxylic acid water reducing agent, the research on the phosphate water reducing agent is still in the beginning stage, and the structure and design aspects are still needed to be broken through.
Disclosure of Invention
The invention provides a preparation method of a polyether intermediate containing aldehyde groups and amino groups and application of the polyether intermediate in a phosphate water reducing agent.
The preparation method of the intermediate containing aldehyde group and amino group is obtained by carrying out Michael addition reaction on a polyamine monomer and an unsaturated aldehyde monomer, wherein the molar ratio of the polyamine monomer to the unsaturated aldehyde monomer is 1: 1.5-2;
the polyamine monomer is any one of monomers such as ethylenediamine, propylenediamine, butylenediamine, pentylenediamine, hexylenediamine, cyclohexanediamine, p-phenylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine and pentaethylenehexamine;
the unsaturated aldehyde monomer has a structure shown as the following formula II:
wherein R1, R2 and R3 each represent a hydrogen atom or a methyl group, and may be the same or different.
Preferably, the unsaturated aldehyde monomer is any one of acrolein, methacrolein, 2-butenal, 3-methyl-2-butenal, 2-methyl-2-butenal, and 2, 3-dimethyl-2-butenal.
The unsaturated aldehyde monomer is more preferably acrolein, methacrolein, 2-butenal.
The preparation method of the intermediate containing aldehyde group and amino group comprises the steps of inducing a polyamine monomer and an unsaturated aldehyde monomer to generate Michael addition reaction under the action of a catalyst, decompressing and vacuumizing after the reaction is finished, evaporating excessive unsaturated aldehyde monomer, and filtering to remove insoluble substances to obtain the intermediate containing aldehyde group and amino group.
The catalyst is strong acid cation resin, such as NKC-9, Amberlyst-15, etc., which can be regenerated and reused, the catalytic efficiency is high, and the dosage of the catalyst is 1-1.5% of the mass of the polyamine monomer
The Michael addition reaction of the polyamine monomer and the unsaturated aldehyde monomer induced by the catalyst is a solvent-free reaction, the temperature is 40-80 ℃, and the reaction pressure is the self pressure of a reaction system;
the reaction time of the Michael addition reaction of the polyamine monomer and the unsaturated aldehyde monomer induced by the catalyst is 1-6 h.
The intermediate containing aldehyde group and amino group is subjected to substitution reaction with chlorinated polyether to obtain a polyether macromonomer containing aldehyde group and amino group; the molar ratio of the chlorinated polyether to the intermediate containing aldehyde groups and amino groups is (0.6-1): 1.
The polyether chain of the chlorinated polyether is obtained by ring-opening reaction of ethylene oxide and/or ethylene oxide, and the weight average molecular weight of the polyether chain is 600-3000.
Such substitution reactions, which are common reactions in organic chemistry, are well known to practitioners in the art. In the method reported by the reference (patent CN 105504297A), water is used as a reaction medium, and the added water accounts for 30-60% of the mass of the chlorinated polyether.
The preparation method of the chlorinated polyether is well known to those skilled in the art, and the reference in the invention reports (Heweidong, synthesis and evaluation of polyether sulfonate [ D ],2011, China university of Petroleum) that the chlorinated polyether with a chlorinated structure is obtained by reacting monoalkoxy polyether with thionyl chloride (SOCl 2).
The substitution reaction is carried out at the reaction temperature of 100-140 ℃ for 8-15 h, and the reaction pressure is the self pressure of the system.
The polyether macromonomer containing aldehyde group and amino group is used for preparing the phosphate water reducing agent.
The phosphate water reducing agent is obtained by performing Mannich reaction on the polyether macromonomer containing aldehyde group and amino group and phosphorous acid and aldehyde monomer under the action of a phosphorylation catalyst and then neutralizing.
The phosphorylation catalyst is a strong acid catalyst, and the catalyst is one or a mixture of more of concentrated hydrochloric acid, concentrated sulfuric acid, methanesulfonic acid, trifluoromethanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid and the like;
the amount of the catalyst is equal to the mass of the polyamine monomer in the synthesis process of the intermediate containing aldehyde group and amine group.
The aldehyde monomer is any one of formaldehyde, trioxymethylene or paraformaldehyde. From the viewpoint of cost and easiness of reaction operation, it is preferable to use 37% by weight of formaldehyde as the aldehyde monomer used in the present invention.
In the Mannich reaction, the molar ratio of the nitrogen atom number, phosphorous acid and aldehyde monomer in polyamine is n: (1-1.1) [ n x + (n +1) × (1-x) ]: (1-1.2) [ (n-1) × x + n (1-x) ], wherein x is the molar ratio of the addition of the chlorinated polyether to the polyamine, and the ratio of the chlorinated polyether to the polyamine obtained by simplification is n: (1-1.1) (n + 1-x): (1-1.2) (n-x).
The Mannich reaction is carried out by firstly slowly adding catalyst, then adding phosphorous acid and finally adding aldehyde monomer into the reaction system in a dropwise manner under the conditions of room-temperature water bath cooling and mechanical stirring.
And (3) carrying out Mannich reaction, heating a reaction system to 100-140 ℃, and keeping the reaction time for 6-12 h to obtain the phosphate water reducing agent product.
The neutralization is to neutralize the reaction system to pH 7, then add water to dilute the reaction system to a certain concentration, and generally add water to dilute the water reducing agent to about 30-40% for storage and transportation.
According to the preparation method of the phosphate water reducing agent, the phosphate water reducing agent is obtained by forming a basic net-shaped framework with amino polyether (containing polyamine) by utilizing the property of a multifunctional group of unsaturated aldehyde monomers, and is a three-dimensional polymeric water reducing agent, the water reducing agent has excellent water reducing performance, and is more excellent in slump retaining performance, retarding performance and clay tolerance performance, and the preparation method has the following specific advantages:
the introduction of phosphorous acid adsorption groups breaks through the traditional carboxyl and sulfonic group system, has strong adsorption capacity and shows strong clay resistance, and the characteristic has great performance advantages in the current market environment with poor quality of concrete admixtures and aggregates. The phosphorous acid structure can provide excellent water reduction and simultaneously give consideration to the effects of slump retaining and retarding; the method has the advantages of simple operation of the whole preparation process, low raw material cost, low production energy consumption and industrial prospect of the preparation process.
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.
Molecular weight test conditions: the molecular weights of all polycondensates in the examples of the invention were determined by means of aqueous gel chromatography (GPC) under the following experimental conditions:
gel column: two Shodex SB806+803 chromatographic columns are connected in series;
mobile phase: 0.1 aqueous MNaNO3 solution;
velocity of mobile phase: 1.01 ml/min;
and (3) injection: 20 μ l of 0.5% aqueous solution;
a detector: a refractive index detector of Shodex RI-71 type;
standard substance: polyethylene glycol GPC standards (Sigma-Aldrich, molecular weight 1010000, 478000, 263000, 118000, 44700, 18600, 6690, 1960, 628, 232).
In the application example of the invention, the adopted cement is reference cement (P.042.5), sand is medium sand with fineness modulus Mx of 2.6, and pebbles are continuous graded broken stones with the particle size of 5-20 mm, except for special description. 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 4 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.
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
Putting 88.15 parts of butanediamine, 89.70 parts of acrolein and 1.06 parts of NKC-9 into a reaction bottle, heating to 55 ℃, stirring for reaction for 3.5 hours, decompressing and vacuumizing after the reaction is finished, evaporating excessive acrolein, and filtering to remove insoluble substances to obtain an intermediate containing aldehyde groups and amino groups; continuously adding 360 parts of water and 900 parts of chlorinated polyether (Mn is 1500) into the reaction bottle under the stirring state, heating to 110 ℃, and reacting for 10 hours; after the reaction is finished, cooling to below 80 ℃, continuously and slowly adding 238.24 parts of concentrated hydrochloric acid, 202.70 parts of phosphorous acid and 120.44 parts of formaldehyde solution with the concentration of 37% while stirring, heating to 140 ℃, reacting for 12 hours, after the reaction is finished, neutralizing by using NaOH solution with the mass concentration of 32.5% until the PH is about 7, adding water to dilute to 30% to obtain a brown finished water reducer, and testing by GPC (gel permeation chromatography) to obtain the water reducer with the molecular weight of 25661 and the molecular weight distribution of 1.55.
Example 2
Placing 114.19 parts of cyclohexanediamine, 126.16 parts of methacrolein and 1.26 parts of Amberlyst-15 into a reaction flask, heating to 80 ℃, stirring for reaction for 5 hours, decompressing and vacuumizing after the reaction is finished to evaporate excessive methacrolein, and filtering to remove insoluble substances to obtain an intermediate containing aldehyde groups and amino groups; adding 1031 parts of water and 1875 parts of chloropolyether (Mn 2500) into the reaction flask while stirring, heating to 130 ℃, and reacting for 14.5 h; after the reaction is finished, cooling to below 80 ℃, continuously and slowly adding 114.19 parts of concentrated sulfuric acid, 195.57 parts of phosphorous acid and 116.67 parts of 37% formaldehyde solution under the stirring state, heating to 125 ℃, reacting for 6 hours, after the reaction is finished, neutralizing by using a NaOH solution with the mass concentration of 32.5% until the PH is about 7, adding water to dilute to 30% to obtain a brown finished water reducer, and testing by GPC (gel permeation chromatography) to obtain the water reducer with the molecular weight of 19771 and the molecular weight distribution of 1.61.
Example 3
Placing 103.17 parts of diethylenetriamine, 133.17 parts of 2-butenal and 1.03 parts of NKC-9 into a reaction bottle, heating to 40 ℃, stirring for reaction for 4.5 hours, performing reduced pressure vacuum-pumping after the reaction is finished to remove excessive 2-butenal, and filtering to remove insoluble substances to obtain an intermediate containing aldehyde groups and amino groups; adding 162 parts of water and 540 parts of chlorinated polyether (Mn 600) into the reaction bottle under the stirring state, heating to 105 ℃, and reacting for 8.5 hours; after the reaction is finished, cooling to below 80 ℃, continuously and slowly adding 103.17 parts of methanesulfonic acid, 259.28 parts of phosphorous acid and 175.55 parts of 37% formaldehyde solution under the stirring state, heating to 100 ℃, reacting for 9.5h, after the reaction is finished, neutralizing by using a NaOH solution with the mass concentration of 32.5% until the PH value is about 7, adding water to dilute to 30% to obtain a brown finished water reducer product, and testing by GPC (gel permeation chromatography) to obtain the water reducer with the molecular weight of 11450 and the molecular weight distribution of 1.22.
Example 4
Placing 189.30 parts of tetraethylenepentamine, 95.30 parts of acrolein and 2.46 parts of Amberlyst-15 into a reaction bottle, heating to 65 ℃, stirring for reacting for 6 hours, decompressing and vacuumizing after the reaction is finished to evaporate excessive acrolein, and filtering to remove insoluble substances to obtain an intermediate containing aldehyde groups and amino groups; under the stirring state, 900 parts of water and 2000 parts of chlorinated polyether (Mn ═ 2000) are added into the reaction bottle, the temperature is raised to 140 ℃, and the reaction is carried out for 14 hours; after the reaction is finished, cooling to below 80 ℃, continuously and slowly adding 189.30 parts of trifluoromethanesulfonic acid, 430.50 parts of phosphorous acid and 353.87 parts of formaldehyde solution with the concentration of 37% while stirring, heating to 135 ℃, reacting for 6.5 hours, after the reaction is finished, neutralizing by using NaOH solution with the mass concentration of 32.5% until the PH is about 7, adding water to dilute to 30% to obtain a brown finished water reducer, and testing by GPC (gel permeation chromatography) to obtain the finished water reducer with the molecular weight of 19428 and the molecular weight distribution of 1.38.
Example 5
Putting 60.10 parts of ethylenediamine, 105.14 parts of methacrolein and 0.90 part of NKC-9 into a reaction bottle, heating to 70 ℃, stirring for reaction for 1.5h, decompressing and vacuumizing after the reaction is finished to evaporate excessive methacrolein, and filtering to remove insoluble substances to obtain an intermediate containing aldehyde groups and amino groups; adding 975 parts of water and 1950 parts of chloropolyether (Mn is 3000) into the reaction flask under the stirring state, heating to 105 ℃, and reacting for 9 hours; after the reaction is finished, cooling to below 80 ℃, continuously and slowly adding 60.10 parts of benzenesulfonic acid, 192.70 parts of phosphorous acid and 109.57 parts of formaldehyde solution with the concentration of 37% while stirring, heating to 120 ℃, reacting for 10 hours, after the reaction is finished, neutralizing by using NaOH solution with the mass concentration of 32.5% until the PH is about 7, adding water to dilute to 30% to obtain a brown finished product of the water reducing agent, and testing by GPC (gel permeation chromatography) to obtain the water reducing agent with the molecular weight of 35591 and the molecular weight distribution of 1.64.
Example 6
Placing 232.37 parts of pentaethylenehexamine, 140.18 parts of 2-butenal and 2.79 parts of Amberlyst-15 in a reaction bottle, heating to 60 ℃, stirring for reaction for 3 hours, reducing pressure, vacuumizing and evaporating to remove excessive 2-butenal after the reaction is finished, and filtering to remove insoluble substances to obtain an intermediate containing aldehyde groups and amino groups; under the stirring state, 350 parts of water and 1000 parts of chlorinated polyether (Mn is 1000) are added into the reaction bottle, the temperature is raised to 125 ℃, and the reaction is carried out for 13.5 hours; after the reaction is finished, cooling to below 80 ℃, continuously and slowly adding 232.27 parts of p-toluenesulfonic acid, 511.68 parts of phosphorous acid and 482.91 parts of 37% formaldehyde solution under the stirring state, heating to 105 ℃, reacting for 7 hours, after the reaction is finished, neutralizing by using a NaOH solution with the mass concentration of 32.5% until the PH is about 7, adding water to dilute to 30% to obtain a brown finished water reducer, and testing by GPC (gel permeation chromatography) to obtain the water reducer with the molecular weight of 12640 and the molecular weight distribution of 1.29.
Example 7
Placing 74.12 parts of propylenediamine, 84.09 parts of acrolein and 1.04 parts of NKC-9 into a reaction flask, heating to 45 ℃, stirring for reaction for 2.5 hours, decompressing and vacuumizing after the reaction is finished to evaporate excessive acrolein, and filtering to remove insoluble substances to obtain an intermediate containing aldehyde groups and amino groups; under the stirring state, 144 parts of water and 480 parts of chlorinated polyether (Mn 600) are added into the reaction bottle, the temperature is raised to 130 ℃, and the reaction is carried out for 10.5 hours; after the reaction is finished, cooling to below 80 ℃, continuously and slowly adding 200.32 parts of concentrated hydrochloric acid, 193.03 parts of phosphorous acid and 105.19 parts of formaldehyde solution with the concentration of 37% while stirring, heating to 115 ℃, reacting for 10.5 hours, after the reaction is finished, neutralizing by using NaOH solution with the mass concentration of 32.5% until the PH is about 7, adding water to dilute to 30% to obtain a brown finished product of the water reducing agent, and testing by GPC (gel permeation chromatography) to obtain the water reducing agent with the molecular weight of 10333 and the molecular weight distribution of 1.19.
Example 8
Placing 102.18 parts of pentamethylene diamine, 112.14 parts of methacrolein and 1.02 parts of Amberlyst-15 in a reaction bottle, heating to 80 ℃, stirring for reaction for 1h, decompressing and vacuumizing after the reaction is finished, evaporating excessive methacrolein, and filtering to remove insoluble substances to obtain an intermediate containing aldehyde groups and amino groups; while stirring, 1275 parts of water and 2125 parts of chloropolyether (Mn 2500) are added into the reaction flask, the temperature is raised to 100 ℃, and the reaction is carried out for 8 hours; after the reaction is finished, cooling to below 80 ℃, continuously and slowly adding 102.18 parts of concentrated sulfuric acid, 181.59 parts of phosphorous acid and 104.54 parts of formaldehyde solution with the concentration of 37% while stirring, heating to 130 ℃, reacting for 7.5 hours, after the reaction is finished, neutralizing by using NaOH solution with the mass concentration of 32.5% until the PH is about 7, adding water to dilute to 30% to obtain a brown finished product of the water reducing agent, and testing by GPC (gel permeation chromatography) to obtain the water reducing agent with the molecular weight of 23606 and the molecular weight distribution of 1.52.
Example 9
Placing 108.14 parts of p-phenylenediamine, 126.16 parts of 2-butenal and 1.30 parts of NKC-9 into a reaction bottle, heating to 50 ℃, stirring for reaction for 5 hours, decompressing and vacuumizing after the reaction is finished, evaporating excessive 2-butenal, and filtering to remove insoluble substances to obtain an intermediate containing aldehyde groups and amino groups; under the stirring state, 420 parts of water and 1050 parts of chloropolyether (Mn is 1500) are added into the reaction bottle, the temperature is raised to 135 ℃, and the reaction is carried out for 12 hours; after the reaction is finished, cooling to below 80 ℃, continuously and slowly adding 108.14 parts of methanesulfonic acid, 205.57 parts of phosphorous acid and 109.73 parts of 37% formaldehyde solution under the stirring state, heating to 110 ℃, reacting for 11 hours, after the reaction is finished, neutralizing by using a NaOH solution with the mass concentration of 32.5% until the PH is about 7, adding water to dilute to 30% to obtain a brown finished water reducer, and testing by GPC (gel permeation chromatography) to obtain the water reducer with the molecular weight of 21838 and the molecular weight distribution of 1.56.
Example 10
Placing 146.23 parts of triethylene tetramine, 106.51 parts of acrolein and 1.90 parts of Amberlyst-15 in a reaction bottle, heating to 60 ℃, stirring for reacting for 2 hours, decompressing and vacuumizing after the reaction is finished to remove excessive acrolein, and filtering to remove insoluble substances to obtain an intermediate containing aldehyde groups and amino groups; adding 1568 parts of water and 2850 parts of chloropolyether (Mn is 3000) into the reaction bottle under the stirring state, heating to 120 ℃, and reacting for 13 hours; after the reaction is finished, cooling to below 80 ℃, continuously and slowly adding 146.23 parts of trifluoromethanesulfonic acid, 348.71 parts of phosphorous acid and 297.05 parts of 37% formaldehyde solution under the stirring state, heating to 125 ℃, reacting for 8 hours, after the reaction is finished, neutralizing by using a NaOH solution with the mass concentration of 32.5% until the PH is about 7, adding water to dilute to 30% to obtain a brown finished water reducer product, and testing by GPC (gel permeation chromatography) to obtain the water reducer with the molecular weight of 31100 and the molecular weight distribution of 1.68.
Comparative example 1
Placing 102.18 parts of pentamethylene diamine, 119.15 parts of methacrolein and 1.53 parts of NKC-9 into a reaction bottle, heating to 75 ℃, stirring for reaction for 5.5 hours, decompressing and vacuumizing after the reaction is finished, evaporating excessive methacrolein, and filtering to remove insoluble substances to obtain an intermediate containing aldehyde groups and amino groups; adding 1440 parts of water and 2400 parts of chloropolyether (Mn ═ 4000) into the reaction flask under the stirring state, heating to 115 ℃, and reacting for 9.5 hours; after the reaction is finished, cooling to below 80 ℃, continuously and slowly adding 102.18 parts of benzenesulfonic acid, 216.48 parts of phosphorous acid and 114.76 parts of formaldehyde solution with the concentration of 37% while stirring, heating to 140 ℃, reacting for 15 hours, after the reaction is finished, neutralizing by using NaOH solution with the mass concentration of 32.5% until the pH is about 7, adding water to dilute to 30% to obtain a brown finished water reducer product, and testing by GPC (gel permeation chromatography) to obtain the water reducer with the molecular weight of 65592 and the molecular weight distribution of 1.93.
Comparative example 2
Placing 103.17 parts of diethylenetriamine, 126.16 parts of 2-butenal and 1.13 parts of Amberlyst-15 into a reaction bottle, heating to 40 ℃, stirring for reaction for 4 hours, decompressing and vacuumizing after the reaction is finished, evaporating excessive 2-butenal, and filtering to remove insoluble substances to obtain an intermediate containing aldehyde groups and amino groups; under the stirring state, 855 parts of water and 1900 parts of chlorinated polyether (Mn 2000) are added into the reaction flask continuously, the temperature is raised to 130 ℃, and the reaction is carried out for 6 hours; after the reaction is finished, cooling to below 80 ℃, continuously and slowly adding 103.17 parts of p-toluenesulfonic acid, 225.09 parts of phosphorous acid and 196.33 parts of formaldehyde solution with the concentration of 37% while stirring, heating to 115 ℃, reacting for 8.5h, after the reaction is finished, neutralizing by using NaOH solution with the mass concentration of 32.5% until the PH is about 7, adding water to dilute to 30%, and obtaining a brown finished water reducer product, wherein the molecular weight is 19874 and the molecular weight distribution is 1.65 through GPC (gel permeation chromatography) test.
Comparative example 3
Putting 88.15 parts of butanediamine and 1.06 parts of NKC-9 into a reaction bottle, heating to 55 ℃, stirring for reaction for 3.5 hours, and filtering to remove insoluble substances after the reaction is finished to obtain an intermediate; continuously adding 360 parts of water and 900 parts of chlorinated polyether (Mn is 1500) into the reaction bottle under the stirring state, heating to 110 ℃, and reacting for 10 hours; after the reaction is finished, cooling to below 80 ℃, continuously and slowly adding 238.24 parts of concentrated hydrochloric acid, 202.70 parts of phosphorous acid and 120.44 parts of formaldehyde solution with the concentration of 37% while stirring, heating to 140 ℃, reacting for 12 hours, after the reaction is finished, neutralizing by using NaOH solution with the mass concentration of 32.5% until the PH is about 7, adding water to dilute to 30% to obtain a brown finished water reducer, and testing by GPC (gel permeation chromatography) to obtain the water reducer with the molecular weight of 1823 and the molecular weight distribution of 1.15.
Comparative example 4
Placing 89.70 parts of acrolein and 1.06 parts of NKC-9 into a reaction bottle, heating to 55 ℃, stirring for reaction for 3.5 hours, decompressing and vacuumizing after the reaction is finished to evaporate excessive acrolein, and filtering to remove insoluble substances to obtain an intermediate; continuously adding 360 parts of water and 900 parts of chlorinated polyether (Mn is 1500) into the reaction bottle under the stirring state, heating to 110 ℃, and reacting for 10 hours; after the reaction is finished, cooling to below 80 ℃, continuously and slowly adding 238.24 parts of concentrated hydrochloric acid, 202.70 parts of phosphorous acid and 120.44 parts of formaldehyde solution with the concentration of 37% while stirring, heating to 140 ℃, reacting for 12 hours, after the reaction is finished, neutralizing by using NaOH solution with the mass concentration of 32.5% until the PH is about 7, adding water to dilute to 30% to obtain a brown finished water reducer product, and testing by GPC (gel permeation chromatography) to obtain the water reducer with the molecular weight of 1627 and the molecular weight distribution of 1.09.
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 small molecular water reducing agent of the present invention has not only good dispersing ability for cement, but also good fluidity maintaining ability.
The molecular weight of the polyether of comparative example 1 is 4000, outside the range, because the polyether has a larger molecular weight and the reaction is not sufficient enough, resulting in too fast a loss of net paste fluidity; the reaction time of comparative example 2 was too short, 6h, and the phosphorous acid was added in an insufficient proportion, resulting in too rapid a loss of net slurry fluidity.
In both comparative examples 3 and 4, the intermediate containing aldehyde groups and amine groups is not successfully introduced, and only polyamine monomers or unsaturated aldehyde monomers are respectively added as the intermediate, so that the concrete does not have good fluidity retention capability or cannot play the function of a water reducing agent.
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 experiments show that the small molecular water reducing agent can obtain excellent slump retaining capacity and good retardation effect under a low mixing amount.
The polyether of comparative example 1 had a molecular weight of 4000, resulting in insufficient slump and spread; the reaction time of comparative example 2 was too short of 6 hours, resulting in insufficient slump and spreadability at 120 min.
In both comparative examples 3 and 4, the intermediate containing aldehyde group and amine group is not successfully introduced, and only polyamine monomers or unsaturated aldehyde monomers are respectively added as the intermediate, so that the obtained concrete does not meet the requirements of slump and expansion.
Application example 3
To evaluate the sensitivity of the slump-retaining small molecule superplasticizers of the invention to clay, the fluidity of mortars formulated with sand containing clay 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; 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 experiment shows that the micromolecule water reducing agent has lower sensitivity to clay in sand under lower mixing amount.
The molecular weight of the polyether of comparative example 1 was 4000; the reaction time of comparative example 2 was too short, 6 hours, resulting in too rapid a loss of mortar fluidity.
In comparative examples 3 and 4, the intermediate containing aldehyde group and amine group is not successfully introduced, and only polyamine monomers or unsaturated aldehyde monomers are respectively added as the intermediate, so that the obtained mortar does not meet the fluidity requirement.
Claims (11)
1. The preparation method of the intermediate containing aldehyde groups and amino groups is characterized in that the intermediate is obtained by carrying out Michael addition reaction on a polyamine monomer and an unsaturated aldehyde monomer, wherein the molar ratio of the polyamine monomer to the unsaturated aldehyde monomer is 1: 1.5-2;
the polyamine monomer is any one of monomers such as ethylenediamine, propylenediamine, butylenediamine, pentylenediamine, hexylenediamine, cyclohexanediamine, p-phenylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine and pentaethylenehexamine;
the unsaturated aldehyde monomer has a structure shown as the following formula II:
wherein R1, R2 and R3 each represent a hydrogen atom or a methyl group, and may be the same or different.
2. The method for preparing an intermediate containing aldehyde groups and amine groups according to claim 1, wherein the unsaturated aldehyde monomer is any one of acrolein, methacrolein, 2-butenal, 3-methyl-2-butenal, 2-methyl-2-butenal, and 2, 3-dimethyl-2-butenal.
3. The method for preparing the intermediate containing aldehyde groups and amine groups according to claim 1, wherein the method for preparing the intermediate containing aldehyde groups and amine groups comprises the steps of inducing a polyamine monomer and an unsaturated aldehyde monomer to generate Michael addition reaction under the action of a catalyst, removing excess unsaturated aldehyde monomer by vacuum evaporation under reduced pressure after the reaction is finished, and filtering to remove insoluble substances to obtain the intermediate containing aldehyde groups and amine groups;
the catalyst is strong acid cation resin selected from NKC-9 or Amberlyst-15, and the dosage of the catalyst is 1-1.5% of the mass of the polyamine monomer.
4. The preparation method of the intermediate containing aldehyde groups and amino groups according to claim 1, wherein the Michael addition reaction of the polyamine monomer and the unsaturated aldehyde monomer induced by the catalyst is a solvent-free reaction at a temperature of 40-80 ℃ and under the pressure of the reaction system; the reaction time of the Michael addition reaction of the polyamine monomer and the unsaturated aldehyde monomer induced by the catalyst is 1-6 h.
5. The use of the intermediate containing aldehyde groups and amine groups as claimed in claim 1, wherein the intermediate containing aldehyde groups and amine groups is subjected to substitution reaction with chlorinated polyether to obtain a polyether macromonomer containing aldehyde groups and amine groups; the molar ratio of the chlorinated polyether to the intermediate containing aldehyde groups and amino groups is (0.6-1): 1.
6. The use according to claim 5, characterized in that the polyether chain of the chlorinated polyether is obtained by a ring-opening reaction of ethylene oxide and/or ethylene oxide, the polyether chain having a weight-average molecular weight of between 600 and 3000.
7. The application of claim 5, wherein the substitution reaction is carried out at a reaction temperature of 100-140 ℃ for 8-15 h, and the reaction pressure is the system pressure.
8. The use of the intermediate containing aldehyde groups and amine groups as claimed in claim 5, wherein the polyether macromonomer containing aldehyde groups and amine groups is used for the preparation of a phosphate-based water reducing agent.
9. The preparation method of the phosphate water reducing agent is characterized in that the phosphate water reducing agent is obtained by performing Mannich reaction on the polyether macromonomer containing aldehyde group and amino group, phosphorous acid and aldehyde monomer under the action of a phosphorylation catalyst and then neutralizing;
the phosphorylation catalyst is a strong acid catalyst, and the catalyst is one or a mixture of more of concentrated hydrochloric acid, concentrated sulfuric acid, methanesulfonic acid, trifluoromethanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid and the like;
the amount of the catalyst is equal to the mass of polyamine monomer in the synthesis process of the intermediate containing aldehyde group and amino group; the aldehyde monomer is any one of formaldehyde, trioxymethylene or paraformaldehyde;
in the Mannich reaction, the molar ratio of the nitrogen atom number, phosphorous acid and aldehyde monomer in polyamine is n: (1-1.1) (n + 1-x): (1-1.2) (n-x), wherein n is the number of nitrogen atoms in the polyamine.
10. The method of claim 9, wherein the mannich reaction is carried out by slowly adding the catalyst, the phosphorous acid, and the aldehyde monomer dropwise into the reaction system under the conditions of cooling in a room-temperature water bath and mechanical stirring.
11. The method according to claim 10, characterized in that in the Mannich reaction, the reaction system is heated to 100-140 ℃ and the reaction time is kept for 6-12 h, so that the phosphate water reducer product is obtained.
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