CN118027332A - Polycondensation type multi-adsorption-group phosphonate water reducer, preparation method and application thereof - Google Patents
Polycondensation type multi-adsorption-group phosphonate water reducer, preparation method and application thereof Download PDFInfo
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- CN118027332A CN118027332A CN202211359788.6A CN202211359788A CN118027332A CN 118027332 A CN118027332 A CN 118027332A CN 202211359788 A CN202211359788 A CN 202211359788A CN 118027332 A CN118027332 A CN 118027332A
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 127
- 239000003638 chemical reducing agent Substances 0.000 title claims abstract description 96
- 238000002360 preparation method Methods 0.000 title claims abstract description 36
- 238000006068 polycondensation reaction Methods 0.000 title claims abstract description 35
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 title claims abstract description 32
- 239000000178 monomer Substances 0.000 claims abstract description 166
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 44
- 229920000570 polyether Polymers 0.000 claims abstract description 44
- DGTNSSLYPYDJGL-UHFFFAOYSA-N phenyl isocyanate Chemical compound O=C=NC1=CC=CC=C1 DGTNSSLYPYDJGL-UHFFFAOYSA-N 0.000 claims abstract description 29
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 claims abstract description 24
- 150000001412 amines Chemical class 0.000 claims abstract description 23
- 238000006243 chemical reaction Methods 0.000 claims abstract description 23
- 229920000056 polyoxyethylene ether Polymers 0.000 claims abstract description 19
- 229940051841 polyoxyethylene ether Drugs 0.000 claims abstract description 19
- 238000001179 sorption measurement Methods 0.000 claims abstract description 19
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims abstract description 18
- -1 phenyl isocyanate compound Chemical class 0.000 claims abstract description 10
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 claims abstract description 6
- HHLFWLYXYJOTON-UHFFFAOYSA-N glyoxylic acid Chemical compound OC(=O)C=O HHLFWLYXYJOTON-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229920000768 polyamine Polymers 0.000 claims abstract description 6
- 150000001299 aldehydes Chemical class 0.000 claims abstract description 5
- 238000005731 phosphitylation reaction Methods 0.000 claims abstract description 5
- MTJGVAJYTOXFJH-UHFFFAOYSA-N 3-aminonaphthalene-1,5-disulfonic acid Chemical compound C1=CC=C(S(O)(=O)=O)C2=CC(N)=CC(S(O)(=O)=O)=C21 MTJGVAJYTOXFJH-UHFFFAOYSA-N 0.000 claims abstract description 3
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 claims abstract description 3
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims abstract description 3
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 claims abstract description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 22
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 20
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 15
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 10
- DZSGDHNHQAJZCO-UHFFFAOYSA-N 1-isocyanato-3,5-dimethylbenzene Chemical group CC1=CC(C)=CC(N=C=O)=C1 DZSGDHNHQAJZCO-UHFFFAOYSA-N 0.000 claims description 8
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical group C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 6
- MGYGFNQQGAQEON-UHFFFAOYSA-N 4-tolyl isocyanate Chemical group CC1=CC=C(N=C=O)C=C1 MGYGFNQQGAQEON-UHFFFAOYSA-N 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims description 6
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 5
- 239000003377 acid catalyst Substances 0.000 claims description 4
- 239000000010 aprotic solvent Substances 0.000 claims description 4
- 239000000376 reactant Substances 0.000 claims description 4
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical group CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 4
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 4
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 3
- 239000004698 Polyethylene Substances 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- 230000005494 condensation Effects 0.000 claims description 3
- 239000012948 isocyanate Substances 0.000 claims description 3
- 150000002513 isocyanates Chemical class 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
- AQGNVWRYTKPRMR-UHFFFAOYSA-N n'-[2-[2-[2-[2-(2-aminoethylamino)ethylamino]ethylamino]ethylamino]ethyl]ethane-1,2-diamine Chemical compound NCCNCCNCCNCCNCCNCCN AQGNVWRYTKPRMR-UHFFFAOYSA-N 0.000 claims description 3
- 229920000573 polyethylene Polymers 0.000 claims description 3
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 claims description 3
- 239000003054 catalyst Substances 0.000 claims description 2
- 238000006482 condensation reaction Methods 0.000 claims description 2
- 125000003916 ethylene diamine group Chemical group 0.000 claims description 2
- 238000005580 one pot reaction Methods 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 230000002194 synthesizing effect Effects 0.000 claims description 2
- 239000004568 cement Substances 0.000 abstract description 24
- 239000004567 concrete Substances 0.000 abstract description 20
- 239000004927 clay Substances 0.000 abstract description 16
- 239000000654 additive Substances 0.000 abstract description 5
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 abstract description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 33
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 18
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 13
- 239000004576 sand Substances 0.000 description 13
- 238000001816 cooling Methods 0.000 description 12
- 238000002156 mixing Methods 0.000 description 12
- 229920005646 polycarboxylate Polymers 0.000 description 12
- 238000010438 heat treatment Methods 0.000 description 11
- 239000002253 acid Substances 0.000 description 8
- 239000004575 stone Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 7
- 239000002270 dispersing agent Substances 0.000 description 6
- 230000014759 maintenance of location Effects 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- ORILYTVJVMAKLC-UHFFFAOYSA-N adamantane Chemical compound C1C(C2)CC3CC1CC2C3 ORILYTVJVMAKLC-UHFFFAOYSA-N 0.000 description 4
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229910052901 montmorillonite Inorganic materials 0.000 description 4
- 239000003431 cross linking reagent Substances 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 238000005227 gel permeation chromatography Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 239000004570 mortar (masonry) Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000008030 superplasticizer Substances 0.000 description 3
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 150000003242 quaternary ammonium salts Chemical group 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229960001124 trientine Drugs 0.000 description 2
- LBLYYCQCTBFVLH-UHFFFAOYSA-N 2-Methylbenzenesulfonic acid Chemical compound CC1=CC=CC=C1S(O)(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 239000002969 artificial stone Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000740 bleeding effect Effects 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000012986 chain transfer agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000002734 clay mineral Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000005357 flat glass Substances 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
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- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
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- 239000004579 marble Substances 0.000 description 1
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- 230000035699 permeability Effects 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
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- 235000010344 sodium nitrate Nutrition 0.000 description 1
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Landscapes
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention belongs to the technical field of concrete additives, and particularly discloses a polycondensation type multi-adsorption-group phosphonate water reducer, a preparation method and application thereof. The polycondensation type multi-adsorption phosphonate water reducer is prepared by carrying out polycondensation and phosphitylation reaction on a monomer A, a monomer B, a monomer C and phosphorous acid; the monomer A is a phenyl isocyanate compound with a polyamine structure, and is prepared by reacting a phenyl isocyanate monomer with an amine monomer; the monomer B is a phenyl isocyanate compound with long-chain polyether, and is prepared by reacting a phenyl isocyanate monomer with a methoxy polyoxyethylene ether monomer; the monomer C is aldehyde monomer selected from formaldehyde, acetaldehyde, glyoxylic acid and benzaldehyde. The reaction condition is simple and easy to operate, and the obtained water reducer has stable structural performance. Because the main chain of the water reducer contains the phosphonic acid adsorption group, the water reducer has better clay resistance, is insensitive to cement-based admixture components, and has strong adaptability to cement and good slump retaining performance.
Description
Technical Field
The invention belongs to the technical field of concrete additives, and particularly relates to a polycondensation type multi-adsorption-group phosphonate water reducer, a preparation method and application thereof.
Background
The concrete is an artificial stone which is designed by taking cementing materials, coarse and fine aggregates and water as basic raw materials according to the mixing ratio. The performance of the concrete can be effectively improved by adding proper additives into the concrete. The admixture is one of indispensable components of modern concrete, and is an important method and technology for modifying concrete. Whereas water reducing agents are one of the most commonly used additives in concrete, in the recent decades of development history of water reducing agents, three stages of development from ordinary water reducing agents, high-efficiency water reducing agents and high-performance water reducing agents have been experienced. The polycarboxylate water reducer is taken as the latest generation water reducer, and is a comb-shaped structure molecule with carboxyl containing negative electricity groups as a main chain and polyether as a long side chain. The long side chain polyether structure of the polycarboxylate water reducer can provide effective steric hindrance and prevent agglomeration among cement particles, so that the dispersion performance of the water reducer is greatly improved. The polycarboxylate water reducer has the advantages of low mixing amount, high water reducing rate, adjustable molecular structure, environment friendliness and the like, and becomes the most important product in the existing additive market for concrete.
The volume ratio of aggregate in concrete is 60% -70%, and the annual consumption of sand and stone is very large. High-quality sand aggregate is more and more scarce, the deterioration trend of the sand aggregate is more and more obvious, and soil is a common harmful component in sand. The too high clay mineral content in the sand stone can lead to the decrease of the strength and the durability of the concrete, and can obviously increase the shrinkage of the concrete. However, the adaptability between the polycarboxylate water reducer and the concrete raw material has been an important reason for restricting the wide use of the polycarboxylate water reducer.
In order to solve the compatibility problem of the polycarboxylic acid water reducer to cement types and sandstone aggregates and the clay tolerance problem, engineering technicians and researchers carry out modification research on the level of the molecular structure of the water reducer based on research theory.
The patent CN201811480337.1 discloses a polycarboxylic acid water reducer, a preparation method and application thereof, wherein an adamantane-containing structural unit substance and an unsaturated monomer with double bonds are reacted according to the mol ratio of 1:1-1:1.5 to obtain an unsaturated adamantane derivative with double bonds; then mixing unsaturated carboxylic acid monomer, unsaturated polyoxyethylene ether monomer and unsaturated adamantane derivative, adding deionized water and emulsifier, stirring and dissolving, adding initiator and chain transfer agent, reacting for 4-6 hours at 50-80 ℃, cooling to room temperature after finishing the reaction, and regulating PH to be neutral by alkali solution to obtain the clay-resistant polycarboxylate superplasticizer. The clay-resistant polycarboxylate superplasticizer has excellent clay-resistant performance, good dispersing capacity, fluidity maintaining capacity, low mixing amount and high water reducing rate.
Patent CN202110028666.8 discloses a preparation method of a novel polycarboxylate superplasticizer with high mud resistance and high slump retention. The novel high-mud-resistance high-slump-retaining polycarboxylate water reducer is prepared by the following steps: (1) preparing an anti-mud crosslinking agent. (2) polymerization. According to the invention, the novel high-mud-resistance high-slump-retention polycarboxylate water reducer with a micro-crosslinking structure is obtained by further polymerizing the prepared anti-mud crosslinking agent with the quaternary ammonium salt structure, the micro-crosslinking structure with the quaternary ammonium salt can effectively improve the dispersion performance of water reducer molecules, the steric hindrance can be increased, the intercalation effect of the water reducer molecules in the clay structure can be reduced, and the mud resistance of the water reducer is enhanced, so that the adaptability of the water reducer to different sand aggregates is improved. And the ester group in the synthesized anti-mud cross-linking agent structure can be gradually hydrolyzed in the cement paste, so that on one hand, the carboxyl in the water reducing agent chain is increased, the slump retaining performance of the water reducing agent chain is improved, and on the other hand, the released micromolecular hydroxyl quaternary ammonium salt molecules are better anti-mud sacrificial agent molecules, so that the anti-mud effect of the water reducing agent can be further improved, and the anti-mud effect is achieved in a long time. The water reducer can also be used as a regulator in machine-made sand concrete.
Patent CN104387536a provides a preparation method of a high water-reducing and clay-resistant polycarboxylic acid cement dispersant, which comprises the following two steps: (1) Free radical polymerization is carried out on a polyether macromonomer, an unsaturated monomer containing sulfonic acid groups and an unsaturated monomer containing ester bonds in an aqueous solution to obtain a dispersant precursor with a molecular weight of 20,000-150,000; (2) And (2) carrying out hydrolysis reaction of ester bonds contained in the dispersant precursor obtained in the step (1) to obtain the polycarboxylic acid cement dispersant. The obtained polycarboxylic acid cement dispersant has good dispersing effect and excellent clay-resistant performance.
The above patent only introduces other modifying monomers on the basis of the polycarboxylic acid water reducer, the main structure of the polycarboxylic acid water reducer is not greatly changed, and the clay-resistant performance of the polycarboxylic acid water reducer is improved only by the modification.
Disclosure of Invention
In order to solve the problems in the prior art mentioned in the background art, the invention provides a polycondensation type multi-adsorption-group phosphonate water reducer, a preparation method and application thereof.
In order to solve the technical problems, the invention provides the following technical scheme:
A polycondensation type multi-adsorption phosphonate water reducer is prepared by carrying out polycondensation and phosphitylation reactions on a monomer A, a monomer B, a monomer C and phosphorous acid.
The molar ratio of the monomer A to the monomer B to the monomer C to the phosphorous acid is as follows: monomer a/monomer b=0.5:1-3:1, monomer C/(monomer a+monomer b+phosphorous acid) =1.1-1.3;
The monomer A is a phenyl isocyanate compound with a polyamine structure, and is prepared by reacting a phenyl isocyanate monomer with an amine monomer; the phenyl isocyanate monomer is selected from phenyl isocyanate, 4-methylphenyl isocyanate, 3, 5-dimethylphenyl isocyanate, diphenylmethane diisocyanate and toluene diisocyanate; the amine monomer is selected from ethylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, hexaethyleneheptamine and polyethylene polyamine.
The monomer B is a phenyl isocyanate compound with long-chain polyether, and is prepared by reacting a phenyl isocyanate monomer with a methoxy polyoxyethylene ether monomer; the isocyanate is selected from phenyl isocyanate, 4-methylphenyl isocyanate, 3, 5-dimethylphenyl isocyanate, diphenylmethane diisocyanate and toluene diisocyanate; the mass fraction of the methoxy polyoxyethylene ether monomer is Mn=1000-8000.
The monomer C is aldehyde monomer selected from formaldehyde, acetaldehyde, glyoxylic acid and benzaldehyde.
The weight average molecular weight of the polycondensation type multi-adsorption-group phosphonate water reducer is 10000-28000.
The invention also provides a preparation method of the polycondensation type multi-adsorption-group phosphonate water reducer, which specifically comprises the following steps:
(1) Preparation of monomer A: adding aprotic solvent, phenyl isocyanate monomer and amine monomer into a dry flask, and reacting for 2-8h at 60-120 ℃ to obtain polycondensable amino monomer, namely monomer A.
(2) Preparation of monomer B: adding phenyl isocyanate monomer and methoxy polyoxyethylene ether monomer into a dry flask, and reacting for 2-8h at 80-130 ℃ to obtain polycondensable polyether macromonomer, namely monomer B.
(3) And (3) synthesizing a polycondensation phosphonate water reducer: and (2) adding the monomer, the phosphorous acid, the aldehyde monomer, the protonic acid catalyst and water obtained in the step (1) and the step (2) into a reaction kettle, and carrying out condensation and phosphitylation reaction at 100-140 ℃ by adopting a one-pot method, and reacting for 6-24h to obtain the polycondensation type multi-adsorption-group phosphonate water reducer.
The aprotic solvent in the step (1) is one of N, N-dimethylformamide and dimethyl sulfoxide, and the solvent content is 30-70% of the total reactant mass.
The molar ratio of the isocyanate monomer to the amine monomer in the step (1) is 1:1-1.5:1.
The molar ratio of the methoxy polyoxyethylene ether monomer to the phenyl isocyanate monomer in the step (2) is 1:1-1:1.1.
The proton acid catalyst in the step (3) is one of sulfuric acid, phosphoric acid and p-toluenesulfonic acid, and the catalyst content accounts for 5-20% of the mass of the reactant.
The molar ratio of phosphorous acid to-N-H in monomer A in step (3) is 0.5:1 to 1.1:1.
The invention also provides application of the polycondensation type multi-adsorption-based phosphonate water reducer, the obtained polycondensation type multi-adsorption-based phosphonate water reducer has good adaptability to cement and admixture as a cement-based material dispersing agent, good clay resistance, good dispersion performance and slump retention performance, and the mixing amount (folding and fixing mixing amount) is 1-5 per mill of the mass of the cementing material when in use, and the specific mixing amount is determined according to actual engineering requirements. However, when the mixing amount is less than 1 per mill, the dispersibility is poor, the engineering requirement cannot be met, when the mixing amount exceeds 5 per mill, the cost performance is low, and segregation and bleeding can occur when the mixing amount is too high.
Compared with the prior art, the invention has the following beneficial effects:
according to the invention, phenyl isocyanate groups respectively react with hydroxyl groups in polyether and amine groups in amine monomers to obtain condensable polyether monomers and condensable amine monomers, and condensation and phosphorous acid reaction are carried out on the condensable polyether monomers and the condensable amine monomers with formaldehyde and phosphorous acid to obtain the polycondensation type multi-adsorption phosphonate water reducer. The reaction condition is simple and easy to operate, and the obtained water reducer has stable structural performance. Due to the introduction of the phenylisocyanate, the long benzene ring skeleton in the main chain ensures that the water reducer has better hydrophobic gas permeability and has better clay resistance due to the strong adsorption property of the phosphonic acid group, is insensitive to cement-based admixture components, and has strong adaptability to cement and good slump retaining property. The polycondensation type multi-adsorption phosphonate water reducer can be used independently, and can also be used in combination with other water reducers on the market.
Detailed Description
For a better understanding of the present invention, the following examples are set forth to illustrate the present invention further, but are not to be construed as limiting the present invention. All equivalent changes or modifications made in accordance with the spirit of the invention should be construed to be within the scope of the present invention.
In the examples of the present invention, the molecular weight of the condensate was measured by Wyatt technology corporation Gel Permeation Chromatography (GPC). The experimental conditions were as follows:
gel column: shodex SB806+803 two chromatographic columns are connected in series;
Washing liquid: 0.1M NaNO3 solution;
mobile phase velocity: 1.0mL/min;
injection: 20uL of 0.5% aqueous solution;
A detector: shodex RI-71 type differential refractor;
Standard substance: polyethylene glycol GPC standard (Sigma-Aldrich, molecular weight 1010000,478000,263000,118000,44700,18600,6690,1960,826,232).
The cement used is 42.5R.P. II, 42.5R.P.O, 42.5 P.O, 42.5 P.5 P.O, and 42.5 PO of Zhong Shan. The fluidity of the cement paste was measured on a plate glass after stirring for 3 minutes with an amount of 87g of water added according to GB/T8077-2000 standard. The mortar test uses 750g of standard cement, 247.5g of water and 1350g of standard sand.
Example 1
Preparation of condensable polyether monomer: 100g of methoxy polyoxyethylene ether with the molecular weight Mn=2000 is added into a 250mL flask, the temperature is raised to 100 ℃, 6.545g of phenyl isocyanate is added dropwise, and the reaction is carried out for 4 hours to obtain the polycondensable polyether monomer.
Preparation of condensable amino monomers: into a 250mL three-neck flask, 42g of dimethyl sulfoxide, 6.1g of ethylenediamine, heating to 80 ℃, dropwise adding 11.9g of phenyl isocyanate, and reacting for 6 hours to obtain a polycondensable carboxyl monomer.
And (3) preparing a water reducer: pouring the condensable polyether monomer and the condensable amine-based monomer into a 500mL flask, adding 100g of water, 41g of phosphorous acid and 15.3g of sulfuric acid, heating to 120 ℃, dropwise adding 28.8g of formaldehyde with 37% concentration, reacting for 12h, cooling, and then adding water and NaOH to adjust the pH to 5 to obtain the water reducer S1 with the molecular weight Mn=15356.
Example 2
Preparation of condensable polyether monomer: 100g of methoxy polyoxyethylene ether with the molecular weight Mn=1000 is added into a 250mL flask, the temperature is raised to 130 ℃, 14.7g of 3, 5-dimethylphenyl isocyanate is added dropwise, and the reaction is carried out for 2 hours to obtain a polycondensable polyether monomer.
Preparation of condensable amino monomers: 50g of N, N-dimethylformamide, 23.2g of hexamethylenediamine, 29.4g of 3, 5-dimethylphenyl isocyanate and the mixture were added into a 250mL three-neck flask and heated to 120℃to react for 2 hours to obtain a polycondensable carboxyl monomer.
And (3) preparing a water reducer: pouring the condensable polyether monomer and the condensable amine-based monomer into a 500mL flask, adding 100g of water, 54.12g of phosphorous acid, 29g of sulfuric acid, heating to 130 ℃, dropwise adding 61.6g of 37% concentration, reacting for 6 hours, cooling, and then adding water and NaOH to adjust the pH to 5 to obtain the water reducer S2 with the molecular weight Mn=11232.
Example 3
Preparation of condensable polyether monomer: 300g of methoxy polyoxyethylene ether with the molecular weight Mn=3000 is added into a 500mL flask, the temperature is raised to 80 ℃, 12.50g of phenyl isocyanate is added dropwise, and the reaction is carried out for 8 hours to obtain a polycondensable polyether monomer.
Preparation of condensable amino monomers: into a 250mL three-necked flask, 21.59g of dimethyl sulfoxide, 20.62g of diethylenetriamine are added, the temperature is raised to 60 ℃, 29.75g of phenyl isocyanate is added dropwise, and the reaction is carried out for 8 hours, thus obtaining a polycondensable carboxyl monomer.
And (3) preparing a water reducer: pouring the condensable polyether monomer and the condensable amine-based monomer into a 1000mL flask, adding 300g of water, 52.48g of phosphorous acid and 24.8g of sulfuric acid, heating to 120 ℃, dropwise adding 80.67g with 37% concentration, reacting for 18h, cooling, adding water and NaOH, and adjusting pH to 5 to obtain the water reducer S3 with the molecular weight Mn= 18357.
Example 4
Preparation of condensable polyether monomer: 100g of methoxypolyoxyethylene ether with a molecular weight Mn=2000 is added into a 250mL flask, the temperature is raised to 100 ℃, 7.35g of 3, 5-dimethylphenyl isocyanate is added dropwise, and the reaction is carried out for 5 hours to obtain a polycondensable polyether monomer.
Preparation of condensable amino monomers: into a 250mL three-neck flask, 30g of N, N-dimethylformamide, 14.6g of triethylene tetramine are added, the temperature is heated to 90 ℃, 19.95g of 4-methylphenyl isocyanate is added dropwise, and the reaction is carried out for 3 hours, so that a carboxyl monomer capable of being polycondensed is obtained.
And (3) preparing a water reducer: pouring the condensable polyether monomer and the condensable amine-based monomer into a 500mL flask, adding 100g of water, 24.6g of phosphorous acid, 20g of sulfuric acid, heating to 100 ℃, dropwise adding 44.60g of 37% concentration, reacting for 24 hours, cooling, and then adding water and NaOH to adjust the pH to 5 to obtain the water reducer S4, wherein the molecular weight Mn=16424.
Example 5
Preparation of condensable polyether monomer: 200g of methoxy polyoxyethylene ether with a molecular weight Mn=4000 is added into a 250mL flask, the temperature is raised to 90 ℃, 5.95g of phenyl isocyanate is added dropwise, and the reaction is carried out for 6 hours to obtain a polycondensable polyether monomer.
Preparation of condensable amino monomers: 30g of dimethyl sulfoxide and 18.93g of tetraethylenepentamine are added into a 250mL three-neck flask, heated to 120 ℃, 12.5g of diphenylmethane diisocyanate is added dropwise, and the reaction is carried out for 3 hours, thus obtaining a carboxyl monomer capable of being polycondensed.
And (3) preparing a water reducer: pouring the condensable polyether monomer and the condensable amine-based monomer into a 1000mL flask, adding 200g of water, 24.6g of phosphorous acid and 24.46g of sulfuric acid, heating to 110 ℃, dropwise adding 43.78g of 37% concentration, reacting for 16h, cooling, and then adding water and NaOH to adjust the pH to 5 to obtain the water reducer S5, wherein the molecular weight Mn= 21319.
Example 6
Preparation of condensable polyether monomer: 200g of methoxy polyoxyethylene ether with a molecular weight Mn=8000 is added into a 250mL flask, the temperature is raised to 110 ℃, 3.325g of 4-methylphenyl isocyanate is added dropwise, and the reaction is carried out for 4 hours to obtain a polycondensable polyether monomer.
Preparation of condensable amino monomers: 50g of dimethyl sulfoxide, 23.8g of pentaethylenehexamine, and 19.95g of 4-methylphenyl isocyanate were added dropwise to a 250mL three-neck flask and reacted for 7 hours to obtain a polycondensable carboxyl monomer.
And (3) preparing a water reducer: pouring the condensable polyether monomer and the condensable amine-based monomer into a 1000mL flask, adding 200g of water, 28.7g of phosphorous acid, 30g of sulfuric acid, heating to 120 ℃, dropwise adding 42.56g of 37% concentration, reacting for 10 hours, cooling, and then adding water and NaOH to adjust the pH to 5 to obtain the water reducer S6, wherein the molecular weight Mn= 26548.
Example 7
Preparation of condensable polyether monomer: 100g of methoxy polyoxyethylene ether with the molecular weight Mn=2000 is added into a 250mL flask, the temperature is raised to 100 ℃, 6.55g of phenyl isocyanate is added dropwise, and the reaction is carried out for 3 hours to obtain a polycondensable polyether monomer.
Preparation of condensable amino monomers: 50g of dimethyl sulfoxide, 55g of polyethylene polyamine, 29.4g of 3, 5-dimethylphenyl isocyanate and the mixture are added into a 250mL three-neck flask and heated to 70 ℃ for 5 hours to obtain a carboxyl monomer capable of being polycondensed.
And (3) preparing a water reducer: pouring the condensable polyether monomer and the condensable amine-based monomer into a 500mL flask, adding 100g of water, 57.4g of phosphorous acid and 30g of phosphoric acid, heating to 130 ℃, dropwise adding 77.43g of 37% concentration, reacting for 16h, cooling, and then adding water and NaOH to adjust the pH to 5 to obtain the water reducer S7, wherein the molecular weight Mn= 16778.
Example 8
Preparation of condensable polyether monomer: 200g of methoxypolyoxyethylene ether with a molecular weight Mn=1000 is added into a 250mL flask, the temperature is raised to 100 ℃, 29.40g of 3, 5-dimethylphenyl isocyanate is added dropwise, and the reaction is carried out for 4 hours to obtain a polycondensable polyether monomer.
Preparation of condensable amino monomers: 50g of dimethyl sulfoxide, 28.7g of hexaethylene heptamine, which is heated to 90 ℃, 17.85g of phenyl isocyanate, which is added dropwise, are added into a 250mL three-neck flask, and the reaction is carried out for 5 hours, so that a carboxyl monomer capable of being polycondensed is obtained.
And (3) preparing a water reducer: the condensable polyether monomer and the condensable amine-based monomer are poured into a 1000mL flask, 200g of water, 65.6g of phosphorous acid and 87g of toluene sulfonic acid are added, the temperature is raised to 140 ℃, 93.24g of formaldehyde with 37% concentration is added dropwise, the reaction is carried out for 6 hours, after cooling, water and NaOH are added to adjust the pH to 5, and the water reducer S8 with the molecular weight Mn=13261 is obtained.
Example 9
Preparation of condensable polyether monomer: 100g of methoxy polyoxyethylene ether with the molecular weight Mn=2000 is added into a 250mL flask, the temperature is raised to 90 ℃, 5.95g of phenyl isocyanate is added dropwise, and the reaction is carried out for 5 hours to obtain a polycondensable polyether monomer.
Preparation of condensable amino monomers: into a 250mL three-necked flask, 20g of N, N-dimethylformamide and 10.31g of diethylenetriamine are added, the temperature is raised to 100 ℃, 8.7g of toluene diisocyanate is added dropwise, and the reaction is carried out for 4 hours, thus obtaining a carboxyl monomer capable of being polycondensed.
And (3) preparing a water reducer: pouring the condensable polyether monomer and the condensable amine-based monomer into a 500mL flask, adding 100g of water, 20.5g of phosphorous acid and 18g of sulfuric acid, heating to 120 ℃, dropwise adding 35.67g of formaldehyde with the concentration of 37%, reacting for 24 hours, cooling, and then adding water and NaOH to adjust the pH to 5 to obtain the water reducer S9 with the molecular weight Mn= 16458.
Example 10
Preparation of condensable polyether monomer: 150g of methoxy polyoxyethylene ether with a molecular weight Mn=2000 is added into a 250mL flask, the temperature is raised to 100 ℃, 9.38g of diphenylmethane diisocyanate is added dropwise, and the reaction is carried out for 4 hours to obtain a polycondensable polyether monomer.
Preparation of condensable amino monomers: 30g of dimethyl sulfoxide, 9.02g of ethylenediamine, and 18.75g of diphenylmethane diisocyanate were added dropwise to a 250mL three-neck flask and reacted for 3 hours to obtain a polycondensable carboxyl monomer.
And (3) preparing a water reducer: pouring the condensable polyether monomer and the condensable amine-based monomer into a 500mL flask, adding 200g of water, 36.9g of phosphorous acid, 28g of sulfuric acid, heating to 120 ℃, dropwise adding 54.73g of formaldehyde with the concentration of 37%, reacting for 16h, cooling, and then adding water and NaOH to adjust the pH to 5 to obtain the water reducer S10 with the molecular weight Mn=16844.
Example 11
Preparation of condensable polyether monomer: 100g of methoxy polyoxyethylene ether with the molecular weight Mn=2000 is added into a 250mL flask, the temperature is raised to 100 ℃, 5.95g of phenyl isocyanate is added dropwise, and the reaction is carried out for 4 hours to obtain a polycondensable polyether monomer.
Preparation of condensable amino monomers: 30g of dimethyl sulfoxide, 15.47g of diethylenetriamine and 17.85g of phenyl isocyanate are added dropwise into a 250mL three-neck flask and reacted for 3 hours to obtain a carboxyl monomer capable of being polycondensed.
And (3) preparing a water reducer: pouring the condensable polyether monomer and the condensable amine-based monomer into a 500mL flask, adding 100g of water, 24.6g of phosphorous acid, 20g of sulfuric acid, heating to 120 ℃, dropwise adding 48.31g of formaldehyde with the concentration of 37%, reacting for 12h, cooling, and then adding water and NaOH to adjust the pH to 5 to obtain the water reducer S11, wherein the molecular weight Mn= 17395.
Comparative example
As a comparative sample, a commercially available polycarboxylate water reducer was designated as S12, having a molecular weight mn= 26253.
Application examples
And (3) carrying out a cement adaptability test on the synthetic water reducer, and respectively carrying out a paste cleaning test on the cement of the benchmark, the field, zhong Shan, the crane forest and the conch, and testing the initial fluidity and the loss with time.
Table 1 cement-adaptive paste fluidity evaluation table
As can be seen from Table 1, the polycondensation type multi-adsorption-based phosphonate water reducer prepared by the invention has good dispersibility when the mixing amount is 0.12%, and has the advantages of large initial fluidity, good adaptability to cement, good slump retention and small fluidity loss after 1 h. While comparative example S12 exhibited unstable fluidity in different cements and had poor adaptability to cements.
Clay resistance experiments are carried out on the synthesized water reducer samples, standard sand and standard cement are used, montmorillonite with different doping amounts is respectively added for experiments, the doping amounts of the water reducer are 0.12%, and the results are shown in table 2:
TABLE 2 comparative testing of the fluidity of mortar in clear slurry with different montmorillonite contents
As can be seen from the results of table 2, all the synthetic samples showed better flowability and slump retention properties in the montmorillonite-containing net-slurry and mortar experiments. The synthesized polycondensation type multi-adsorption-group phosphonate water reducer has better clay resistance.
According to the test method of the high-performance water reducer in the standard of the national standard GB8076-2008 concrete admixture, the adopted cement is the field 525.5 R.P.II cement, the sand is the medium sand with the fineness modulus Mx=2.6, the stones are small stones with the grain size of 5-10mm and large stones with the grain size of 10-20mm, continuous graded broken stones are used as materials, and the indexes such as dispersibility, clay resistance, gas content, slump retention capacity and the like of the water reducer are tested according to the proportions specified in the table 3, and the test results are shown in the table 4. The blending amount of each example was 0.24%.
TABLE 3 concrete mix for testing
| Raw materials | Small field cement | Sand and sand | Small stone | Marble stone | Water and its preparation method |
| The ratio of kg/m3 | 400 | 886 | 380 | 570 | 174 |
Table 4 table for evaluating the properties of the concrete
The concrete fluidity data in table 4 shows that the synthesized polycondensation type multi-adsorption-based phosphonate water reducer has better dispersibility and slump retention property than the polycarboxylate water reducer in the comparative example, has stronger clay resistance, and also shows better working performance in the concrete stirring process, and the possible reason is that the air entraining performance of the long benzene ring structure in the main chain structure of the water reducer leads to better working performance of the concrete. The phosphonic acid group has strong adsorptivity, so that the phosphonic acid group is less influenced by montmorillonite and has stronger clay resistance.
Claims (11)
1. A polycondensation type multi-adsorption phosphonate water reducer is prepared by carrying out polycondensation and phosphitylation reaction on a monomer A, a monomer B, a monomer C and phosphorous acid;
The monomer A is a phenyl isocyanate compound with a polyamine structure, and is prepared by reacting a phenyl isocyanate monomer with an amine monomer;
The monomer B is a phenyl isocyanate compound with long-chain polyether, and is prepared by reacting a phenyl isocyanate monomer with a methoxy polyoxyethylene ether monomer;
The monomer C is an aldehyde monomer selected from formaldehyde, acetaldehyde, glyoxylic acid and benzaldehyde;
The molar ratio of the monomer A to the monomer B to the monomer C to the phosphorous acid is as follows: monomer a/monomer b=0.5:1-3:1, monomer C/(monomer a+monomer b+phosphorous acid) =1.1-1.3.
2. The polycondensation type multi-adsorption phosphonate water reducing agent according to claim 1, wherein the phenyl isocyanate monomers for preparing the monomer A and the monomer B are independently selected from phenyl isocyanate, 4-methylphenyl isocyanate, 3, 5-dimethylphenyl isocyanate, diphenylmethane diisocyanate and toluene diisocyanate.
3. The polycondensation, multi-adsorptive phosphonate water reducer of claim 1, wherein the amine monomer is selected from the group consisting of ethylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, hexaethyleneheptamine, and polyethylene polyamine.
4. The polycondensation type multi-adsorption-based phosphonate water reducer according to claim 1, wherein the mass fraction of the methoxy polyoxyethylene ether monomer is mn=1000-8000.
5. The polycondensation type multi-adsorptive phosphonate water reducing agent according to claim 1, wherein the weight average molecular weight of the polycondensation type multi-adsorptive phosphonate water reducing agent is 10000-28000.
6. The method for preparing the polycondensation type multi-adsorption-based phosphonate water reducing agent according to any one of claims 1 to 5, which is characterized by comprising the following steps:
(1) Preparation of monomer A: adding aprotic solvent, phenyl isocyanate monomer and amine monomer into a dry flask, and reacting for 2-8 hours at 60-120 ℃ to obtain polycondensable amino monomer, namely monomer A;
(2) Preparation of monomer B: adding phenyl isocyanate monomer and methoxy polyoxyethylene ether monomer into a dry flask, and reacting for 2-8 hours at 80-130 ℃ to obtain polycondensable polyether macromonomer, namely monomer B;
(3) And (3) synthesizing a polycondensation phosphonate water reducer: and (2) adding the monomer, the phosphorous acid, the aldehyde monomer, the protonic acid catalyst and water obtained in the step (1) and the step (2) into a reaction kettle, and carrying out condensation and phosphitylation reaction at 100-140 ℃ by adopting a one-pot method, and reacting for 6-24h to obtain the polycondensation type multi-adsorption-group phosphonate water reducer.
7. The method for preparing the polycondensation type multi-adsorption-based phosphonate water reducer according to claim 6, wherein the aprotic solvent in the step (1) is one of N, N-dimethylformamide and dimethyl sulfoxide, and the solvent content is 30% -70% of the total reactant mass.
8. The method for preparing the polycondensation type multi-adsorption phosphonate water reducing agent according to claim 6, wherein the molar ratio of isocyanate monomer to amine monomer in the step (1) is 1:1-1.5:1.
9. The method for preparing the polycondensation type multi-adsorption-based phosphonate water reducer according to claim 6, wherein the molar ratio of the methoxy polyoxyethylene ether monomer to the phenyl isocyanate monomer in the step (2) is 1:1-1:1.1.
10. The method for preparing the polycondensation type multi-adsorption-based phosphonate water reducer according to claim 6, wherein the proton acid catalyst in the step (3) is one of sulfuric acid, phosphoric acid and p-toluenesulfonic acid, and the catalyst content is 5-20% of the mass of the reactants.
11. The method for preparing a polycondensation type multi-adsorption-based phosphonate water reducing agent according to claim 6, wherein the molar ratio of phosphorous acid to-N-H in the monomer A in the step (3) is 0.5:1-1.1:1.
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