CN113968949A - High-adaptability water reducing agent based on biological amino acid and preparation method and application thereof - Google Patents
High-adaptability water reducing agent based on biological amino acid and preparation method and application thereof Download PDFInfo
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- CN113968949A CN113968949A CN202010722158.5A CN202010722158A CN113968949A CN 113968949 A CN113968949 A CN 113968949A CN 202010722158 A CN202010722158 A CN 202010722158A CN 113968949 A CN113968949 A CN 113968949A
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- reducing agent
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 96
- 239000003638 chemical reducing agent Substances 0.000 title claims abstract description 80
- 150000001413 amino acids Chemical class 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- OUYCCCASQSFEME-QMMMGPOBSA-N L-tyrosine Chemical compound OC(=O)[C@@H](N)CC1=CC=C(O)C=C1 OUYCCCASQSFEME-QMMMGPOBSA-N 0.000 claims abstract description 43
- OUYCCCASQSFEME-UHFFFAOYSA-N tyrosine Natural products OC(=O)C(N)CC1=CC=C(O)C=C1 OUYCCCASQSFEME-UHFFFAOYSA-N 0.000 claims abstract description 43
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 claims abstract description 28
- 239000000178 monomer Substances 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 16
- ABLZXFCXXLZCGV-UHFFFAOYSA-N phosphonic acid group Chemical group P(O)(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229920000056 polyoxyethylene ether Polymers 0.000 claims abstract description 10
- 229940051841 polyoxyethylene ether Drugs 0.000 claims abstract description 10
- 125000001033 ether group Chemical group 0.000 claims abstract description 9
- 230000026731 phosphorylation Effects 0.000 claims abstract description 9
- 238000006366 phosphorylation reaction Methods 0.000 claims abstract description 9
- 230000008569 process Effects 0.000 claims abstract description 7
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000002253 acid Substances 0.000 claims description 22
- 239000003054 catalyst Substances 0.000 claims description 20
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 19
- 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 19
- 125000000129 anionic group Chemical group 0.000 claims description 16
- 239000002904 solvent Substances 0.000 claims description 14
- 239000008098 formaldehyde solution Substances 0.000 claims description 13
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims description 12
- 239000001257 hydrogen Substances 0.000 claims description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims description 11
- 239000000376 reactant Substances 0.000 claims description 11
- 239000003729 cation exchange resin Substances 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 claims description 9
- 239000003513 alkali Substances 0.000 claims description 9
- -1 polyoxypropylene Polymers 0.000 claims description 9
- 238000001914 filtration Methods 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 8
- 238000006386 neutralization reaction Methods 0.000 claims description 8
- 239000006185 dispersion Substances 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical group [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- 150000001875 compounds Chemical group 0.000 claims description 6
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 5
- YZUPZGFPHUVJKC-UHFFFAOYSA-N 1-bromo-2-methoxyethane Chemical compound COCCBr YZUPZGFPHUVJKC-UHFFFAOYSA-N 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 150000001450 anions Chemical class 0.000 claims description 4
- 238000009833 condensation Methods 0.000 claims description 4
- 230000005494 condensation Effects 0.000 claims description 4
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 4
- 150000002989 phenols Chemical class 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 claims description 4
- 125000000542 sulfonic acid group Chemical group 0.000 claims description 4
- 229940090248 4-hydroxybenzoic acid Drugs 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 229960004889 salicylic acid Drugs 0.000 claims description 3
- 239000004593 Epoxy Substances 0.000 claims description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical class C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical group C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical group [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical class CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 2
- 239000003125 aqueous solvent Substances 0.000 claims description 2
- 238000004821 distillation Methods 0.000 claims description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 2
- 239000003456 ion exchange resin Substances 0.000 claims description 2
- 229920003303 ion-exchange polymer Polymers 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 2
- 239000003495 polar organic solvent Substances 0.000 claims description 2
- 238000006068 polycondensation reaction Methods 0.000 claims description 2
- 229920001451 polypropylene glycol Polymers 0.000 claims description 2
- 239000011591 potassium Chemical group 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 238000004321 preservation Methods 0.000 claims description 2
- 150000003141 primary amines Chemical group 0.000 claims description 2
- 238000007142 ring opening reaction Methods 0.000 claims description 2
- 150000003335 secondary amines Chemical group 0.000 claims description 2
- 239000011734 sodium Chemical group 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 238000004090 dissolution Methods 0.000 claims 1
- 238000002372 labelling Methods 0.000 claims 1
- 238000001179 sorption measurement Methods 0.000 abstract description 8
- 125000000524 functional group Chemical group 0.000 abstract description 5
- 229920000642 polymer Polymers 0.000 abstract description 5
- 238000006482 condensation reaction Methods 0.000 abstract description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract 1
- 239000004568 cement Substances 0.000 description 30
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 11
- 238000012360 testing method Methods 0.000 description 11
- 230000000694 effects Effects 0.000 description 7
- 239000004927 clay Substances 0.000 description 6
- 229910052500 inorganic mineral Inorganic materials 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 239000011707 mineral Substances 0.000 description 6
- 239000002994 raw material Substances 0.000 description 5
- 239000004721 Polyphenylene oxide Substances 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 238000011161 development Methods 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
- 239000000463 material Substances 0.000 description 4
- 229910052901 montmorillonite Inorganic materials 0.000 description 4
- 229920000570 polyether Polymers 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000004566 building material Substances 0.000 description 3
- 239000004567 concrete Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- ZHNFOHFZWIRCNY-UHFFFAOYSA-N 4-ethoxybenzenesulfonic acid Chemical compound CCOC1=CC=C(S(O)(=O)=O)C=C1 ZHNFOHFZWIRCNY-UHFFFAOYSA-N 0.000 description 1
- 238000006683 Mannich reaction Methods 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 1
- 239000011398 Portland cement Substances 0.000 description 1
- 238000003991 Rietveld refinement Methods 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000000740 bleeding effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009440 infrastructure construction Methods 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
- 230000007246 mechanism Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- DGVVJWXRCWCCOD-UHFFFAOYSA-N naphthalene;hydrate Chemical compound O.C1=CC=CC2=CC=CC=C21 DGVVJWXRCWCCOD-UHFFFAOYSA-N 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 description 1
- 150000003009 phosphonic acids Chemical class 0.000 description 1
- 229920001467 poly(styrenesulfonates) Polymers 0.000 description 1
- 229920005646 polycarboxylate Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000011002 quantification Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Inorganic materials [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 1
- 229940006186 sodium polystyrene sulfonate Drugs 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 230000001360 synchronised effect Effects 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G16/00—Condensation polymers of aldehydes or ketones with monomers not provided for in the groups C08G4/00 - C08G14/00
- C08G16/02—Condensation polymers of aldehydes or ketones with monomers not provided for in the groups C08G4/00 - C08G14/00 of aldehydes
- C08G16/0212—Condensation polymers of aldehydes or ketones with monomers not provided for in the groups C08G4/00 - C08G14/00 of aldehydes with acyclic or carbocyclic organic compounds
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/24—Macromolecular compounds
- C04B24/243—Phosphorus-containing polymers
- C04B24/246—Phosphorus-containing polymers containing polyether side chains
-
- C—CHEMISTRY; METALLURGY
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
The invention discloses a high-adaptability water reducing agent based on biological amino acid and a preparation method and application thereof. The structural units of the water reducing agent comprise phosphorylation residues of tyrosine and phenoxy polyoxyethylene ether residues; it is a polymer composed of the structural units arranged randomly. The water reducing agent is prepared by carrying out phosphorylation-condensation reaction on tyrosine, phenoxy polyoxyethylene ether and auxiliary monomers at the same time. The water reducing agent is prepared from biological amino acid, the process is more green and environment-friendly, and the water reducing agent has various adsorption functional groups such as phosphonic acid groups, carboxyl groups, phenolic hydroxyl groups and the like, has excellent water reducing performance and strong adaptability to a gelling system.
Description
Technical Field
The invention relates to a high-adaptability water reducing agent based on biological amino acid, a preparation method and application thereof, belonging to the technical field of building materials.
Technical Field
In recent years, with the rapid promotion of infrastructure construction and the vigorous development of urbanization in China, the requirements of various building materials are rapidly expanded, meanwhile, the compositions of cement and admixtures used for building material concrete are increasingly complicated, and the application of admixtures such as machine-made sand, calcined clay and the like is increased, so that higher requirements are provided for the raw material adaptability of the water reducing agent and the tolerance of a complex gelling system. At present, the mainstream water reducing agents such as naphthalene water reducing agents, polycarboxylic acid water reducing agents and the like have single adsorption groups, have limited universality on different types of cementing materials and strong development adaptability, and the water reducing agents which have stable performances on impurities such as clay and the like in different cementing systems become a new subject of water reducing agent development.
Meanwhile, in recent years, the pursuit of green development and environmental protection also increasingly requires the greening of the production raw materials and the process of the water reducing agent, and the use of the non-toxic and environment-friendly raw materials and the process with low emission and low three wastes become a new trend for developing the water reducing agent in the future.
Under the above background, in recent years, some reports have been made about water reducing agents containing novel functional groups, especially phosphonic acid-based water reducing agents, which are the directions of interest for related research and development due to the good adsorption capacity of phosphonic acid groups on various minerals. For example, CN106832147B discloses a preparation method of a phosphonic acid group-containing polycarboxylic acid water reducer, wherein a phosphonic acid group-containing unsaturated alkenyl monomer is added in the preparation process, and a phosphoric acid group is introduced into the structure of the conventional polycarboxylic acid water reducer, so that the slump of the obtained water reducer is maintained, the mud resistance is effectively improved, and the sensitivity of concrete is reduced. CN105152565B reports a polyphosphonic acid water reducing agent and a synthesis method thereof, and the patent is also based on the idea of introducing unsaturated phosphonic acid group monomers in the polymerization process, and the obtained water reducing agent has better slump retention and water reducing performance compared with common polycarboxylic acid. CN103848944B discloses a method for preparing a super-retarding polycarboxylic acid water reducer by using unsaturated polyether, unsaturated carboxylic acid/anhydride, unsaturated sulfonic acid and unsaturated phosphonic acid monomers, wherein the water reducer realizes a super-retarding effect by introducing phosphate.
The water reducing agent still uses a large amount of traditional chemical raw materials as main monomers, so that the production process has the risk of toxicity and high potential risk to the environment. CN107868243A discloses a preparation method of an amino acid-derived phosphorous acid water reducing agent, wherein amino acid-terminated halogenated polyether is used for performing phosphorylation to prepare a phosphonated single polyether chain water reducing agent, the used raw materials are more environment-friendly, but the water reducing efficiency of the single polyether chain water reducing agent is still different from that of a water reducing agent with a comb-shaped polymer structure.
Disclosure of Invention
Under the background, the invention provides a high-adaptability water reducing agent based on biological amino acid and a preparation method and application thereof.
The molecular structural unit of the high-adaptability water reducing agent based on the biological amino acid comprises a phosphorylation residue of tyrosine and a phenoxy polyoxyethylene ether residue; the modified amino acid is a polymer formed by randomly arranging the structural units, and the phosphorylation residue and the phenoxy polyoxyethylene ether residue of the tyrosine are respectively shown as formulas 1-2:
the phosphorylation residue 1 of tyrosine is shown as formula 1, wherein X is hydrogen or sodium, potassium, and X of different groups and units can be independent.
The phenoxy polyoxyethylene ether residue is shown as formula 2, wherein R is1Is a hydrogen atom or a methyl group, and wherein the proportion of hydrogen atoms is not less than 80%, R2Is a C1-C6 hydrocarbyl group;
p1 is a number of 0-10, p2 is a number of 15-60, it should be noted that the polyoxyethylene ether chain segment in the above formula is only marked by noting the type composition of the structural unit in the chain segment, and does not represent the actual arrangement of the polyoxypropylene and polyoxyethylene side chains in the structural unit, and the two types of structures can be arranged and combined in any way including block and random arrangement;
in the high-adaptability water reducing agent based on biological amino acid, each phosphorylated residue of tyrosine contains 3 anionic groups, the number of the phosphorylated residues of tyrosine is m1 in the chain sequence, the high-adaptability water reducing agent also contains an auxiliary anionic chain segment, the number of the phosphorylated residues of tyrosine is m2, m2 can be zero, m1+ m2+ n is 10-200, m1+ m2) n is 2-10, and the mass ratio of the phosphorylated residues of tyrosine to the auxiliary anionic chain segment is (70-100): (30-0);
the auxiliary anionic segment refers to a segment containing an anionic group selected from a sulfonic acid group, a carboxyl group, a phosphonic acid group or a phosphate group.
The weight average molecular weight of the high-adaptability water reducing agent based on the biological amino acid is 6000-40000.
Preferably, the structural formula of the auxiliary anion segment of the high-adaptability water reducing agent based on biological amino acid conforms to the following general formula 3:
the auxiliary anion chain segment is shown as a formula 3, wherein Y is a C0-C8 group containing nitrogen or oxygen atoms directly connected with a benzene ring; z is a C0-C8 group containing at least 1 anionic group; the anionic group is selected from a sulfonic acid group, a carboxyl group, a phosphonic acid group or a phosphate group.
The preparation method of the high-adaptability water reducing agent based on the biological amino acid comprises the following steps: the high-adaptability water reducing agent based on the biological amino acid is prepared by the phosphonic acid reaction of synchronous tyrosine and auxiliary monomers (optional) and phosphorous acid and the polycondensation of the phosphonic acid, phenoxy macromonomer and formaldehyde solution.
The phenoxy macromonomer is a condensation polymerizable macromonomer taking end phenyl or alkylated phenol as an end group and having a polyoxyethylene (propylene) chain structure. The macromonomers can be prepared from phenol and substituted phenols, ethylene oxide and propylene oxide via well-known epoxy compound ring opening processes.
The auxiliary monomer is a compound which has C0-C8 groups containing nitrogen atoms or oxygen atoms directly connected with benzene and at least one anionic C0-C8 group, such as p-hydroxybenzoic acid, salicylic acid and the like.
The dosage of the tyrosine, the auxiliary monomer and the phenoxy macromonomer satisfies the following relationship: the total molar weight of the tyrosine and the auxiliary monomer is 2-10 times of that of the phenoxy macromonomer, and meanwhile, the molar weight of the tyrosine accounts for 70-100% of that of the tyrosine and the auxiliary monomer.
The preparation method of the high-adaptability water reducing agent based on the biological amino acid also uses a catalyst, and the catalyst is a hydrogen type strong-acid ion exchange resin, such as: 732 strong acid cation exchange resin (hydrogen type), Amberlyst-15 type strong acid cation exchange resin. The dosage of the catalyst is 0.6-1.2 times of the mass of the tyrosine.
The preparation method of the high-adaptability water reducing agent based on the biological amino acid comprises the following specific steps:
taking a certain amount of tyrosine, an auxiliary monomer (optional), a phenoxy macromonomer and a catalyst, uniformly mixing in a solvent, adding phosphorous acid, uniformly stirring, slowly adding a formaldehyde solution, and controlling the temperature to be not more than 50 ℃ in the period; then heating to 80-120 ℃, carrying out heat preservation condensation for 2-10 h, and filtering out the catalyst; if the solvent is a non-aqueous solvent, the solvent is recovered by reduced pressure distillation, water with the mass 1.5-3 times that of the obtained product is added for dispersion, and if the solvent is water, the steps of recovering the solvent and adding water for dispersion can be omitted; and adding alkali with the total acid equivalent of the reactant of 0-100% for neutralization to obtain the water reducing agent.
The solvent is water or a polar organic solvent which is favorable for dissolving tyrosine, such as DMSO, and a mixed system of the solvents. The dosage of the catalyst is 1.5 to 4 times of the total mass of reactants except the catalyst, namely tyrosine, auxiliary monomer, phenoxy macromonomer, formaldehyde and phosphorous acid.
In the preparation process, the amount of phosphorous acid used is equal to the molar amount of all active amino hydrogens in the respective monomers, i.e. 2 moles of phosphorous acid per mole of primary amine group and 1 mole of phosphorous acid per mole of secondary amine group.
The formaldehyde solution is a commercial 37 percent product. The dosage of the compound is 0.9-1.1 times of the total molar weight of tyrosine, auxiliary monomer and phenoxy macromonomer participating in the reaction and the sum of the molar weight of active amino hydrogen in the monomers.
The alkali is common inorganic or non-volatile (boiling point >100 ℃) organic tertiary amine, such as sodium hydroxide, potassium hydroxide, sodium carbonate, triethanolamine and the like, and the inorganic alkali is recommended in consideration of cost problems, such as no special application requirements.
In the preparation process, all reactants are subjected to phosphonic Mannich reaction and condensation reaction which are carried out synchronously, and a polymer water reducing agent is obtained through one-pot reaction, wherein the reaction process is as follows:
the invention discloses a synthetic mechanism of a water reducing agent
The invention also discloses an application method of the water reducing agent, the water reducing agent can be used as a dispersing agent for portland cement and concrete, is suitable for a gelling system with a water-cement ratio of 0.2-0.5, has excellent water reducing performance, and has good adaptability to different types of cement. The folding and fixing mixing amount is 0.04-0.25% of the total mass of the rubber material, the dispersion effect is insufficient if the folding and fixing mixing amount is less than the value, no obvious benefit is obtained if the mixing amount is continuously increased if the folding and fixing mixing amount is more than the value, and adverse phenomena such as bleeding, segregation and the like are easy to occur.
The invention has the advantages that:
(1) the non-toxic and environment-friendly biological amino acid tyrosine is used as a precursor of a main structural unit in the water reducer, and the prepared water reducer is high in degradability, greener in production process, safer and more harmless.
(2) Through the innovation of the reaction process, the phosphorylation of the amino acid and the condensation of the water reducing agent are simultaneously carried out, the operation is simple and convenient, and the industrialization is convenient. Meanwhile, the reaction solvent and the catalyst can be recovered, the reaction conversion rate is high, all monomer materials enter the final product, and three wastes are not discharged.
(3) The water reducing agent chain segment contains a plurality of functional groups such as carboxyl, phosphonic acid group, phenolic hydroxyl and the like, the functional groups can realize stronger adsorption on the surface of a mineral phase through synergism, and meanwhile, the adsorption groups are diversified, so that the water reducing agent can be adsorbed with different mineral phases and admixtures, and the adaptability to different mineral compositions and admixture types of gelling systems is better.
Detailed Description
The present invention will be further illustrated with reference to the following examples, but the present invention is not limited to the following examples. All equivalent changes or modifications made according to the spirit of the method of the present invention should be covered within the protection scope of the present invention.
In the examples of the present invention, the molecular weight of the polymer was measured using a Wyatt technology corporation Gel Permeation Chromatograph (GPC). The experimental conditions were as follows: gel column: two Shodex SB806+803 chromatographic columns are connected in series; washing liquid: 0.1M NaNO3A solution; velocity of mobile phase: 1.0 mL/min; and (3) injection: 20uL of 0.5% aqueous solution; a detector: shodex RI-71 type differential refractive index; standard substance: sodium polystyrene sulfonate GPC standard (Sigma-Aldrich, molecular weight 344100,195800,108200,60000,37500,28200,6900, 3000, 1400).
Example 1
130.5 parts by mass of tyrosine, 117.4 parts by mass of 732 type cation exchange resin (hydrogen type) and 328.1 parts by mass of phenoxy macromonomer A-1 are uniformly mixed in 1600 parts by mass of water, 118.1 parts by mass of phosphorous acid is added, the mixture is uniformly stirred, 194.1 parts by mass of formaldehyde solution is slowly added, and the temperature is controlled not to exceed 50 ℃ in the period. And then heating to 100 ℃, condensing for 6h, filtering out the catalyst, adding liquid alkali with the total acid equivalent of the reactant of 80% for neutralization to obtain the water reducing agent P-1 with the weight-average molecular weight of 17.6 kDa.
Example 2
Taking 108.7 parts by mass of tyrosine, 66 parts by mass of 732 type cation exchange resin (hydrogen type) and 226.2 parts by mass of phenoxy macromonomer A-2, uniformly mixing in 2300 parts of water, adding 98.4 parts by mass of phosphorous acid, uniformly stirring, slowly adding 153.2 parts by mass of formaldehyde solution, and controlling the temperature not to exceed 50 ℃ during the period. And then heating to 100 ℃, condensing for 2h, filtering out the catalyst, adding liquid alkali with the total acid equivalent of the reactant of 60% for neutralization to obtain the water reducing agent P-2 with the weight-average molecular weight of 6.7 kDa.
Example 3
Taking 108.7 parts by mass of tyrosine, 10.35 parts by mass of p-hydroxybenzoic acid, 87 parts by mass of 732 type cation exchange resin (hydrogen type) and 313.2 parts by mass of phenoxy macromonomer A-3, uniformly mixing in 1500 parts by mass of water, adding 98.4 parts by mass of phosphorous acid, uniformly stirring, and slowly adding 150.2 parts by mass of formaldehyde solution, wherein the temperature is controlled not to exceed 50 ℃. And then heating to 80 ℃, condensing for 8h, filtering out the catalyst, adding liquid alkali with 80% of total acid equivalent of reactants for neutralization to obtain the water reducing agent P-3 with the weight-average molecular weight of 13.8 kDa.
Example 4
Taking 116.0 parts by mass of tyrosine, 22.1 parts by mass of salicylic acid, 139.2 parts by mass of 732 type cation exchange resin (hydrogen type) and 375.2 parts by mass of phenoxy macromonomer A-4, uniformly mixing in 1500 parts by mass of dimethyl sulfoxide, adding 105.0 parts by mass of phosphorous acid, uniformly stirring, and slowly adding 192.6 parts by mass of formaldehyde solution, wherein the temperature is controlled not to exceed 50 ℃. And then heating to 110 ℃, condensing for 10h, filtering out the catalyst, distilling under reduced pressure to remove dimethyl sulfoxide, adding 1600 parts of water-dispersed water reducing agent, and adding liquid alkali with the total acid equivalent of 100% of reactants for neutralization to obtain the water reducing agent P-4 with the weight-average molecular weight of 37.8 kDa.
Example 5
101.5 parts by mass of tyrosine, 71.3 parts by mass of N, N-dimethyl-phosphonic acid aniline, 106.5 parts by mass of Amberlyst-15 type strong-acid cation exchange resin and 346.4 parts by mass of phenoxy macromonomer A-5 are uniformly mixed in 1600 parts of dimethyl sulfoxide, 91.8 parts by mass of phosphorous acid is added, the mixture is uniformly stirred, 163.8 parts by mass of formaldehyde solution is slowly added, and the temperature is controlled not to exceed 50 ℃ during the process. And then heating to 120 ℃, condensing for 4h, filtering out the catalyst, distilling under reduced pressure to remove dimethyl sulfoxide, adding 1800 parts of water-dispersible water reducing agent, adding sodium carbonate with 40% of total acid equivalent of reactant for neutralization to obtain the water reducing agent P-5 with the weight-average molecular weight of 28.8 kDa.
Example 6
Taking 108.7 parts by mass of tyrosine, 24.3 parts by mass of p-ethoxybenzenesulfonic acid, 108.7 parts by mass of Amberlyst-15 type strong-acid cation exchange resin and 292.1 parts by mass of phenoxy macromonomer A-6, uniformly mixing in 1500 parts of water, adding 98.4 parts by mass of phosphorous acid, uniformly stirring, slowly adding 165.4 parts by mass of formaldehyde solution, and controlling the temperature to be not more than 50 ℃. And then heating to 100 ℃, condensing for 6h, filtering out the catalyst, adding liquid alkali with 60 percent of total acid equivalent of reactants for neutralization to obtain the water reducing agent P-6 with the weight-average molecular weight of 20.6 kDa.
Evaluation of the Properties of examples
First, the dispersing effect of each example on various cements was evaluated by a net slurry fluidity test. The test flow is based on GB/T8077-2000, 300g of cement is used in the test, and the water-cement ratio is 0.29. The cement used is benchmark cement (P.I.42.5), golden corner cement (P.O.42.5), cheng cement (P.O.42.5) and small wild field cement (P.II.52.5). The cement components were determined by XRD quantification (internal standard, Rietveld method). All tests were carried out at 20 degrees, and in order to further confirm the efficacy of each example, a commercial polycarboxylate water reducer of the PCA-I type and a phosphonate water reducer of the HPA type, produced by Jiangsu Subot New materials GmbH, were used. In the test, the breaking admixture amount of all the water reducing agents including the examples and the comparison is 0.10%.
Table 1 examples evaluation tests of the type and composition of the cements used
TABLE 2 Dispersion Performance in terms of Net-spread (mm) for various examples and comparative examples for different types of cement paste
The percentage of the sample of the example obtained by subtracting the lowest value from the highest value of the fluidity in each cement and dividing by the lowest value is indicative of the fluctuation of the water reducing capacity of the example for different cements.
As can be seen from the above table, the fluidity of each cement paste sample doped in each example is higher than that of the PCA-I and HPA type water reducing agents used as comparison, especially for golden corner cement, and the fluidity of each cement is stable, and the difference of the fluidity is not more than 15% at most, which is obviously lower than that of the carboxylic acid type water reducing agent and is also lower than that of the phosphonic acid type water reducing agent used as comparison. The water reducer disclosed by the invention has various adsorption functional groups and can ensure effective adsorption on different mineral phases, and the results prove the dispersing performance of each embodiment on cement. Meanwhile, after 60min, the fluidity of the cement paste blended with each example was only slightly reduced, which indicates that each example has good slump-retaining property at the same time.
On the basis of the test, the clay tolerance of each embodiment is also tested, the test is also carried out in a net slurry test mode, and in the test, montmorillonite with the mass of 1.0% of the cement is used for replacing the cement. The examples and the control were tested for the dispersing effect on cement, and the results were as follows:
TABLE 3 Dispersion performance of each example and comparative example on different kinds of cement paste containing 1% of montmorillonite, expressed as paste spread (mm)
From the above results, it can be seen that the dispersing effect of each example on cement neat paste containing 1% montmorillonite is reduced compared to cement without montmorillonite, but the reduction is much lower than that of PCA-I and HPA as controls, especially PCA-I, which lose the initial dispersing effect on the gold corner cement after doping with 1% clay and 60min dispersing effect on cement systems other than the Anthrig cement. The clay tolerance of the embodiment of the invention is to ensure that the multifunctional water reducing agent disclosed by the invention is more closely adsorbed and combined with the mineral phase and is not easily caused by the competitive adsorption failure of the clay.
In conclusion, the results of the application tests prove that the water reducer disclosed by the invention has high adaptability and excellent efficiency.
Claims (10)
1. A high-adaptability water reducing agent based on biological amino acid is characterized in that the molecular structural unit of the high-adaptability water reducing agent comprises phosphorylation residues of tyrosine and phenoxy polyoxyethylene ether residues; the tyrosine phosphorylation residue and the phenoxy polyoxyethylene ether residue are respectively shown as formulas 1-2:
the phosphorylation residue 1 of tyrosine is shown as formula 1, wherein X is hydrogen or sodium, potassium, and X of different groups and units are independent;
the phenoxy polyoxyethylene ether residue is shown as formula 2, wherein R is1Is a hydrogen atom or a methyl group, and wherein the proportion of hydrogen atoms is not less than 80%, R2Is a C1-C6 hydrocarbyl group;
p1 is a number of 0-10, p2 is a number of 15-60, the labeling mode of the polyoxyethylene ether chain segment in the above formula is only the type composition of the structural unit in the noted chain segment, and does not represent the actual arrangement mode of the polyoxypropylene and polyoxyethylene side chains in the structural unit, and the two types of structures can be arranged and combined in any mode including block and random arrangement.
2. The water reducing agent with high adaptability based on biological amino acids as claimed in claim 1, characterized in that each phosphorylated residue of tyrosine contains 3 anionic groups, the number of phosphorylated residues of tyrosine is m1 in the chain sequence, the water reducing agent also contains auxiliary anionic chain segments, the number of phosphorylated residues of tyrosine is m2, m2 can be zero, m1+ m2+ n is within 10-200, and (m1+ m2): n is within 2-10, and the mass ratio of phosphorylated residues of tyrosine and the auxiliary anionic chain segments is (70-100): (30-0);
the auxiliary anionic segment refers to a segment containing an anionic group selected from a sulfonic acid group, a carboxyl group, a phosphonic acid group or a phosphate group.
3. The high-adaptability water reducing agent based on biological amino acid as claimed in claim 1 or 2, wherein the weight average molecular weight of the high-adaptability water reducing agent based on biological amino acid is 6000-40000.
4. The bio-amino acid based high-adaptability water reducing agent according to claim 2, characterized in that the structural formula of the auxiliary anion segment of the bio-amino acid based high-adaptability water reducing agent is in accordance with the following general formula 3:
the auxiliary anion chain segment is shown as a formula 3, wherein Y is a C0-C8 group containing nitrogen or oxygen atoms directly connected with a benzene ring; z is a C0-C8 group containing at least 1 anionic group; the anionic group is selected from a sulfonic acid group, a carboxyl group, a phosphonic acid group or a phosphate group.
5. The method for preparing the high-adaptability water reducing agent based on biological amino acid according to any one of claims 1 to 4, characterized in that the high-adaptability water reducing agent based on biological amino acid is prepared by simultaneous phosphonation of tyrosine and auxiliary monomers (optional) with phosphorous acid and simultaneous polycondensation with phenoxy macromonomer and formaldehyde solution;
the phenoxy macromonomer is a condensable macromonomer which takes end phenyl or alkylated phenol as an end group and has a polyoxyethylene (propylene) chain structure; the macromonomer is prepared from phenol and substituted phenol, ethylene oxide and propylene oxide through a well-known epoxy compound ring opening process;
the auxiliary monomer is a compound which has C0-C8 groups containing nitrogen atoms or oxygen atoms directly connected with benzene and contains at least one anionic C0-C8 group, such as p-hydroxybenzoic acid and salicylic acid;
the dosage of the tyrosine, the auxiliary monomer and the phenoxy macromonomer satisfies the following relationship: the total molar weight of the tyrosine and the auxiliary monomer is 2-10 times of that of the phenoxy macromonomer, and meanwhile, the molar weight of the tyrosine accounts for 70-100% of that of the tyrosine and the auxiliary monomer.
6. The method according to claim 5, characterized in that the preparation method of the high-adaptability water reducing agent based on biological amino acids further uses a catalyst which is a strong acid ion exchange resin in hydrogen form, such as 732 strong acid cation exchange resin (hydrogen form), Amberlyst-15 strong acid cation exchange resin; the dosage of the catalyst is 0.6-1.2 times of the mass of the tyrosine.
7. The method according to claim 5 or 6, characterized in that the method for preparing the high-adaptability water reducing agent based on the biological amino acid comprises the following steps:
taking a certain amount of tyrosine, optional auxiliary monomers, phenoxy macromonomers and catalysts, uniformly mixing in a solvent, adding phosphorous acid, uniformly stirring, slowly adding a formaldehyde solution, and controlling the temperature to be not more than 50 ℃; then heating to 80-120 ℃, carrying out heat preservation condensation for 2-10 h, and filtering out the catalyst; if the solvent is a non-aqueous solvent, the solvent is recovered by reduced pressure distillation, water with the mass 1.5-3 times that of the obtained product is added for dispersion, and if the solvent is water, the steps of recovering the solvent and adding water for dispersion can be omitted; and adding alkali with the total acid equivalent of the reactant of 0-100% for neutralization to obtain the high-adaptability water reducing agent based on the biological amino acid.
8. The method according to claim 7, wherein the solvent is water or a polar organic solvent which facilitates the dissolution of tyrosine, and a mixed system of these solvents; the dosage of the catalyst is 1.5-4 times of the total mass of reactants except the catalyst, namely tyrosine, auxiliary monomer, phenoxy macromonomer, formaldehyde and phosphorous acid.
9. A process according to claim 7 wherein the phosphorous acid is used in an amount equal to the molar amount of all active amino hydrogens in each monomer, i.e. 2 moles phosphorous acid per mole primary amine group and 1 mole phosphorous acid per mole secondary amine group.
10. The method of claim 7, wherein the formaldehyde solution is a commercially available 37% formaldehyde solution. The dosage of the compound is 0.9-1.1 times of the total molar weight of tyrosine, auxiliary monomer and phenoxy macromonomer participating in the reaction and the sum of the molar weight of active amino hydrogen in the monomers.
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