CN114014788A - Chain transfer agent for polycarboxylate superplasticizer, application and preparation method thereof - Google Patents
Chain transfer agent for polycarboxylate superplasticizer, application and preparation method thereof Download PDFInfo
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- CN114014788A CN114014788A CN202111188698.0A CN202111188698A CN114014788A CN 114014788 A CN114014788 A CN 114014788A CN 202111188698 A CN202111188698 A CN 202111188698A CN 114014788 A CN114014788 A CN 114014788A
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- chain transfer
- transfer agent
- water reducing
- polycarboxylate superplasticizer
- polycarboxylic acid
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- 239000012986 chain transfer agent Substances 0.000 title claims abstract description 53
- 229920005646 polycarboxylate Polymers 0.000 title claims abstract description 48
- 239000008030 superplasticizer Substances 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 52
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 39
- 239000002253 acid Substances 0.000 claims abstract description 32
- 239000000126 substance Substances 0.000 claims abstract description 24
- FRPDXUHZSXRSCC-UHFFFAOYSA-N amino benzenesulfonate Chemical compound NOS(=O)(=O)C1=CC=CC=C1 FRPDXUHZSXRSCC-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000003054 catalyst Substances 0.000 claims abstract description 14
- 238000007112 amidation reaction Methods 0.000 claims abstract description 11
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 9
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 49
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical group C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 15
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 13
- 238000006467 substitution reaction Methods 0.000 claims description 12
- -1 4-aminomethyl benzene sulfonic acid sodium Chemical compound 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 7
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 229940006193 2-mercaptoethanesulfonic acid Drugs 0.000 claims description 4
- NQAAZYRPQDGORT-UHFFFAOYSA-N 2-sulfanylpropane-1-sulfonic acid Chemical compound CC(S)CS(O)(=O)=O NQAAZYRPQDGORT-UHFFFAOYSA-N 0.000 claims description 4
- ZNEWHQLOPFWXOF-UHFFFAOYSA-N coenzyme M Chemical compound OS(=O)(=O)CCS ZNEWHQLOPFWXOF-UHFFFAOYSA-N 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- KSVSZLXDULFGDQ-UHFFFAOYSA-M sodium;4-aminobenzenesulfonate Chemical compound [Na+].NC1=CC=C(S([O-])(=O)=O)C=C1 KSVSZLXDULFGDQ-UHFFFAOYSA-M 0.000 claims description 4
- 229910006069 SO3H Inorganic materials 0.000 claims description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 3
- 229910001510 metal chloride Inorganic materials 0.000 claims description 3
- 229910044991 metal oxide Inorganic materials 0.000 claims description 3
- 150000004706 metal oxides Chemical class 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- RIHPJWMGFBFKFC-UHFFFAOYSA-N 4-aminobenzenesulfonic acid;potassium Chemical compound [K].NC1=CC=C(S(O)(=O)=O)C=C1 RIHPJWMGFBFKFC-UHFFFAOYSA-N 0.000 claims description 2
- NGSZMAVBHNFAAB-UHFFFAOYSA-N 2,4-diaminobenzenesulfonic acid;potassium Chemical compound [K].NC1=CC=C(S(O)(=O)=O)C(N)=C1 NGSZMAVBHNFAAB-UHFFFAOYSA-N 0.000 claims 1
- ZSBCZEFDYNLRQQ-UHFFFAOYSA-N 2,4-diaminobenzenesulfonic acid;sodium Chemical compound [Na].NC1=CC=C(S(O)(=O)=O)C(N)=C1 ZSBCZEFDYNLRQQ-UHFFFAOYSA-N 0.000 claims 1
- 238000009826 distribution Methods 0.000 abstract description 8
- 230000015572 biosynthetic process Effects 0.000 abstract description 7
- 238000012546 transfer Methods 0.000 abstract description 6
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- 238000006116 polymerization reaction Methods 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 15
- 239000000243 solution Substances 0.000 description 11
- 238000004519 manufacturing process Methods 0.000 description 9
- 239000004721 Polyphenylene oxide Substances 0.000 description 7
- 239000012452 mother liquor Substances 0.000 description 7
- 229920000570 polyether Polymers 0.000 description 7
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 6
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 6
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 6
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 5
- 239000010413 mother solution Substances 0.000 description 5
- 239000004576 sand Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000011049 filling Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- SZHIIIPPJJXYRY-UHFFFAOYSA-M sodium;2-methylprop-2-ene-1-sulfonate Chemical compound [Na+].CC(=C)CS([O-])(=O)=O SZHIIIPPJJXYRY-UHFFFAOYSA-M 0.000 description 4
- 150000003573 thiols Chemical class 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 3
- 239000004568 cement Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000004575 stone Substances 0.000 description 3
- PXQLVRUNWNTZOS-UHFFFAOYSA-N sulfanyl Chemical class [SH] PXQLVRUNWNTZOS-UHFFFAOYSA-N 0.000 description 3
- 239000011592 zinc chloride Substances 0.000 description 3
- 235000005074 zinc chloride Nutrition 0.000 description 3
- 239000011787 zinc oxide Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229960005070 ascorbic acid Drugs 0.000 description 2
- 235000010323 ascorbic acid Nutrition 0.000 description 2
- 239000011668 ascorbic acid Substances 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 229960002089 ferrous chloride Drugs 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 description 2
- OISKOTDBNZTYCS-UHFFFAOYSA-M potassium;2,4-diaminobenzenesulfonate Chemical compound [K+].NC1=CC=C(S([O-])(=O)=O)C(N)=C1 OISKOTDBNZTYCS-UHFFFAOYSA-M 0.000 description 2
- LDZHTQSBXDDUFB-UHFFFAOYSA-M potassium;4-aminobenzenesulfonate Chemical compound [K+].NC1=CC=C(S([O-])(=O)=O)C=C1 LDZHTQSBXDDUFB-UHFFFAOYSA-M 0.000 description 2
- 229940077386 sodium benzenesulfonate Drugs 0.000 description 2
- WYSWTEPAYPNWDV-UHFFFAOYSA-M sodium;2,4-diaminobenzenesulfonate Chemical compound [Na+].NC1=CC=C(S([O-])(=O)=O)C(N)=C1 WYSWTEPAYPNWDV-UHFFFAOYSA-M 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical group OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000007405 data analysis Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000003754 machining Methods 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
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- JUSKCLXHKSPSFV-UHFFFAOYSA-M sodium;4-(aminomethyl)benzenesulfonate Chemical compound [Na+].NCC1=CC=C(S([O-])(=O)=O)C=C1 JUSKCLXHKSPSFV-UHFFFAOYSA-M 0.000 description 1
- MZSDGDXXBZSFTG-UHFFFAOYSA-M sodium;benzenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C1=CC=CC=C1 MZSDGDXXBZSFTG-UHFFFAOYSA-M 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- IIACRCGMVDHOTQ-UHFFFAOYSA-M sulfamate Chemical compound NS([O-])(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-M 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- OBSZRRSYVTXPNB-UHFFFAOYSA-N tetraphosphorus Chemical compound P12P3P1P32 OBSZRRSYVTXPNB-UHFFFAOYSA-N 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000006276 transfer reaction Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
- C07C323/64—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and sulfur atoms, not being part of thio groups, bound to the same carbon skeleton
- C07C323/67—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and sulfur atoms, not being part of thio groups, bound to the same carbon skeleton containing sulfur atoms of sulfonamide groups, bound to the carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/16—Sulfur-containing compounds
- C04B24/20—Sulfonated aromatic compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
- C07C319/02—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of thiols
- C07C319/12—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of thiols by reactions not involving the formation of mercapto groups
-
- 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)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention relates to the technical field of concrete admixtures, in particular to a chain transfer agent for a polycarboxylic acid water reducing agent, and application and a preparation method thereof. The chain transfer agent for the polycarboxylate superplasticizer is prepared by carrying out amidation reaction on aminobenzenesulfonate and functional sulfydryl substances under the catalysis of a catalyst. The chain transfer agent for the polycarboxylate superplasticizer has the structure containing sulfydryl and benzenesulfonic groups, can improve the water solubility and the chain transfer catalytic performance in a polymerization reaction, can be used as the chain transfer agent in the synthesis of the polycarboxylate superplasticizer, can better adjust the molecular weight of the polycarboxylate superplasticizer, has narrow molecular weight distribution of the polycarboxylate superplasticizer participating in the synthesis, and can obviously improve the flowing property, slump retaining property and compressive strength of concrete after the polycarboxylate superplasticizer acts on the concrete.
Description
Technical Field
The invention relates to the technical field of concrete admixtures, in particular to a chain transfer agent for a polycarboxylic acid water reducing agent, and application and a preparation method thereof.
Background
Polycarboxylic acid water reducers are continuously developed and evolved from the original aliphatic water reducers, sulfamate water reducers, naphthalene water reducers and the third generation polycarboxylic acid water reducers developed to the present. The polycarboxylic acid water reducing agent produced in the current market can be divided into a water reducing type, a slump retaining type, an ultra-slow release type, an early strength type, a viscosity reduction type and the like in performance, and has the advantages of mature production technology, relatively simple production process, economy, applicability, diversified and controllable molecular structure, higher water reducing rate of concrete under the condition of low mixing amount and the like, so that the polycarboxylic acid water reducing agent becomes one of indispensable additives in the current market.
The chain transfer agent is one of important components in the production of the polycarboxylic acid water reducing agent, and has the function of adjusting the molecular weight of the polycarboxylic acid. The chain transfer agent is reasonably utilized, the molecular weight of the polycarboxylate superplasticizer can be adjusted, and the production cost can be reduced. At present, chain transfer agents for polycarboxylic acid water reducing agents in the market are mercaptoacids, thiol substances and hypophosphite, but the mercaptoacids have strong pungent smell and strong volatility, so that the production of the polycarboxylic acid water reducing agents is greatly disturbed, and the production requirement of environmental protection is not met. In recent years, the price of raw materials such as yellow phosphorus is continuously high, and hypophosphite is easy to deliquesce and is easy to explode when meeting strong oxidants, so that great potential safety hazards are left for the production of the polycarboxylic acid water reducing agent. And according to related reports: the large amount of thiol species causes the initial reaction to form a number of dead linear oligomers without pendant double bonds; in the later stage of the reaction, the concentration of thiol substances is reduced, the chain transfer reaction is correspondingly reduced, the molecular weight of the formed polymer is very high, the molecular weight distribution of the polymer is very wide, and the quality accident of the production is caused because some reaction systems are even directly crosslinked to form gel.
The application number is CN201110334937.9, and the published application is Chinese invention application of 2012, 06, 20 and discloses a method for preparing a polycarboxylate water reducer by using sodium methallyl sulfonate as a chain transfer agent, which comprises the following steps: adding water, sodium methallyl sulfonate and modified polyether into a reaction kettle, mixing the sodium methallyl sulfonate, acrylic acid and the water to prepare an acrylic acid solution, mixing the water and ammonium persulfate to prepare an ammonium persulfate solution, starting to simultaneously dropwise add the ammonium persulfate solution and the acrylic acid solution when the temperature of the materials reaches 60 +/-2 ℃, carrying out heat preservation reaction for 1-3 h, cooling to below 45 ℃, adding 32% liquid alkali for neutralization, and obtaining the polycarboxylic acid water reducing agent with the pH value of 6-7 and the solid content of 40%. Because the sodium methallyl sulfonate is adopted to replace thioglycollic acid or mercaptopropionic acid as a chain transfer agent in the preparation process of the polycarboxylate superplasticizer, the pollution to the environment and the toxic action to a human body caused by the foul smell and strong corrosivity of the mercaptopropionic acid or thioglycollic acid can be avoided.
Disclosure of Invention
In order to solve the problems of the prior chain transfer agent in the synthesis process of the polycarboxylate superplasticizer in the background art: the invention provides a chain transfer agent for a polycarboxylate water reducing agent, which has the following structural general formula:
wherein M is Na+Or K+The substitution position of R is-SO on the benzene ring3At least one of ortho position, meta position and para position of the M group has 1-3 substitution numbers, and the structural general formula of R is as follows:
wherein n is 2 to 3.
In one embodiment, the compound is prepared by performing amidation reaction on aminobenzenesulfonate and functional sulfydryl substances under the catalysis of a catalyst; 5-15 parts of aminobenzenesulfonate, 10-20 parts of functional sulfydryl substances and 0.01-0.1 part of catalyst by weight.
In one embodiment, the structural formula of the aminobenzenesulfonate is:
wherein M is Na+、K+，R1is-NH2、-CH2NH2、-CH2CH2NH2,R1The substitution position is-SO on the benzene ring3At least one of the ortho position, the meta position and the para position of M, and the number of substitution is 1-3.
In one embodiment, the aminobenzenesulfonate is one or more of sodium 4-aminobenzenesulfonate, potassium 4-aminobenzenesulfonate, sodium 2, 4-diaminobenzenesulfonate, potassium 2, 4-diaminobenzenesulfonate, sodium 4-aminomethylbenzenesulfonate, potassium 4-aminomethylbenzenesulfonate, sodium 2, 4-diaminomethylbenzenesulfonate, and potassium 2, 4-diaminomethylbenzenesulfonate.
In one embodiment, the functional sulfydryl substance has a general structural formula:
wherein R is2is-COOH, -SO3H and n are 2-3.
In one embodiment, the functional mercapto substance is one or more of thioglycolic acid, mercaptopropionic acid, 2-mercaptoethanesulfonic acid and 2-mercaptopropanesulfonic acid.
In one embodiment, the catalyst is one or more of metal chloride and metal oxide.
The invention also provides the application of the chain transfer agent for the polycarboxylate superplasticizer, wherein the chain transfer agent for the polycarboxylate superplasticizer is used as a chain transfer agent in the synthesis reaction of the polycarboxylate superplasticizer.
The invention also provides a preparation method of the chain transfer agent for the polycarboxylate superplasticizer, which comprises the following steps:
s100, adding aminobenzene sulfonate and a catalyst into a reaction kettle, stirring and mixing, and introducing inert gas to fill the reaction kettle until the amidation reaction is finished;
s200, heating the reaction temperature in the reaction kettle to 60-75 ℃, and adding a functional sulfydryl substance;
s300, after the functional sulfydryl substances are added, heating the reaction temperature to 85-105 ℃, and carrying out amidation reaction for a certain time at a constant temperature to obtain the chain transfer agent for the polycarboxylate superplasticizer.
In one embodiment, in S200, the functional mercapto substance is slowly added dropwise into the reaction kettle for 1 to 3 hours; in S300, the amidation reaction time at constant temperature is 1-3 h.
Compared with the prior art, the invention has the following technical effects:
the chain transfer agent for the polycarboxylate superplasticizer provided by the invention contains sulfydryl and benzenesulfonic acid groups in the structure, compared with the strong volatility of a sulfydryl acid chain transfer agent, the volatility of the chain transfer agent is reduced, the water solubility of the chain transfer agent and the chain transfer catalytic performance in a polymerization reaction can be improved, the chain transfer agent can be used as the chain transfer agent in the synthesis of the polycarboxylate superplasticizer, the molecular weight of the polycarboxylate superplasticizer can be better adjusted, the molecular weight distribution of the polycarboxylate superplasticizer participating in the synthesis is narrow, and after the polycarboxylate superplasticizer acts on concrete, the flowing property, slump retaining property and compressive strength of the concrete can be obviously improved, and the healthy development of the polycarboxylate superplasticizer industry is promoted.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings needed to be used in the description of the embodiments or the prior art will be briefly introduced below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to these drawings without creative efforts.
FIG. 1 is a gel permeation chromatogram of a mother solution of a polycarboxylic acid water reducing agent prepared in comparative example 1, provided by the invention;
FIG. 2 is a gel permeation chromatogram of a mother solution of a polycarboxylic acid water reducing agent prepared in example 1 provided by the present invention;
FIG. 3 is a gel permeation chromatogram of a mother solution of a polycarboxylate superplasticizer prepared in example 2 provided by the present invention;
FIG. 4 is a gel permeation chromatogram of a mother solution of a polycarboxylate superplasticizer prepared in example 3 provided by the present invention;
FIG. 5 is a gel permeation chromatogram of a mother solution of a polycarboxylic acid water reducing agent prepared in example 4 provided by the present invention.
Detailed Description
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings needed to be used in the description of the embodiments or the prior art will be briefly introduced below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to these drawings without creative efforts.
The invention provides a preparation method of a chain transfer agent for a polycarboxylate superplasticizer, which comprises the following steps:
(1) weighing aminobenzenesulfonate, a catalyst and functional sulfydryl substances according to a certain weight part;
(2) adding aminobenzenesulfonate and a catalyst into a reaction kettle, stirring for 5-15 min to uniformly mix the raw materials, and introducing inert gas to fill the reaction kettle until the amidation reaction is finished;
(3) heating the reaction temperature in the reaction kettle to 60-75 ℃, and adding functional sulfydryl substances;
(4) after the functional sulfydryl substances are added, the reaction temperature is increased to 85-105 ℃, and amidation reaction is carried out for 1-3 h at constant temperature, so as to prepare the chain transfer agent for the polycarboxylate superplasticizer.
The constant temperature reaction temperature is set to be 85-105 ℃ so as to dehydrate in the chain transfer agent, which is beneficial to forward balance movement of the reaction and improves the conversion rate of the chain transfer agent for the polycarboxylate superplasticizer.
Preferably, the functional sulfydryl substances are slowly dripped into the reaction kettle for 1-3 h, and the slow dripping reaction is more sufficient.
Preferably, the inert gas is nitrogen (N)2)。
The invention also provides the following examples and comparative examples:
example 1
Adding 5 weight parts of sodium 4-aminobenzenesulfonate and 0.01 weight part of zinc oxide into a reaction kettle, stirring for 5min, and introducing N2And filling the whole reaction kettle until the reaction is finished, heating the system in the reaction kettle to 60 ℃, then starting to dropwise add thioglycollic acid in 10 parts by weight, dropwise adding for 1h, heating to 85 ℃, and reacting at constant temperature for 1h to obtain the chain transfer agent for the polycarboxylate superplasticizer.
Example 2
(1) Chain transfer agent for preparing polycarboxylic acid water reducing agent:
adding 8 weight parts of 4-aminobenzenesulfonic acid potassium and 0.04 weight part of zinc chloride into a reaction kettle, stirring for 8min, and introducing N2And filling the whole reaction kettle until the reaction is finished, heating the system in the reaction kettle to 65 ℃, starting to dropwise add 13 parts by weight of 2-mercaptoethanesulfonic acid, heating to 95 ℃ after dropwise adding for 1h, and reacting for 2h at constant temperature to obtain the chain transfer agent for the polycarboxylic acid water reducing agent.
Example 3
Adding 12 weight parts of 4-aminomethyl sodium benzenesulfonate, 0.07 weight part of zinc oxide and zinc chloride (1: 1) into a reaction kettle, stirring for 12min, and introducing N2And filling the whole reaction kettle until the reaction is finished, heating the system in the reaction kettle to 70 ℃, starting to dropwise add 15 parts by weight of mercaptopropionic acid, heating to 100 ℃ after dropwise adding for 1 hour, and reacting at constant temperature for 1.5 hours to obtain the chain transfer agent for the polycarboxylic acid water reducing agent.
Example 4
Adding 15 parts by weight of 2, 4-diaminomethyl sodium benzenesulfonate and 0.1 part by weight of ferrous chloride into a reaction kettle, stirring for 15min, and introducing N2And filling the whole reaction kettle until the reaction is finished, heating the system in the reaction kettle to 75 ℃, starting to dropwise add 20 parts by weight of 2-mercaptopropanesulfonic acid, after dropwise adding for 1h, heating to 105 ℃, and reacting at constant temperature for 3h to obtain the chain transfer agent for the polycarboxylate superplasticizer.
Comparative example 1
Commercially available thioglycolic acid chain transfer agents are provided. Wherein, the mercaptoacetic acid employed in comparative example 1 corresponds to the mercaptoacetic acid starting material employed in example 1.
The chain transfer agents provided in the examples and the comparative examples are synthesized into polycarboxylate superplasticizer mother liquor under the same dosage conditions, and the synthesis method of the polycarboxylate superplasticizer mother liquor is as follows:
adding 195g of modified polyether HPEG, 2g of 27.5% hydrogen peroxide solution and 100g of water into a reaction kettle with a stirrer, raising the temperature in the reaction kettle to 40 ℃, stirring until the solution in the reaction kettle is colorless and transparent, dropwise adding a mixed solution of acrylic acid, ascorbic acid and water (wherein the content of the acrylic acid, the ascorbic acid and the water is 16.5g, 0.3g and 20g respectively), dropwise adding a mixed solution of a chain transfer agent and water (wherein the content of the chain transfer agent and the water is 0.75g and 20g respectively), reacting at constant temperature of 40 ℃ for 2 hours after dropwise adding, adding 5g of solid sodium hydroxide for neutralization reaction, and supplementing 75g of water to obtain 50% polycarboxylic acid water reducer mother liquor. Wherein the modified polyether HPEG is a modified polyether HPEG of brand HPEG-LA888-01 produced by Hubei Lingan science and technology limited company, and the molecular weight of the modified polyether HPEG is 2400.
The polycarboxylate superplasticizer mother liquor prepared in examples 1-4 and comparative example 1 is subjected to molecular weight measurement according to GB/T27843-2011 Gel Permeation Chromatography (GPC) for measuring the content of low molecular weight components in chemical polymers, and the measurement results are shown in the following table 1 and FIGS. 1-5:
TABLE 1GPC data
| Sample numbering | Number average molecular weight Mn | Weight average molecular weight Mw | Peak molecular weight Mp | Polydispersity Mw/Mn |
| Comparative example 1 | 29861 | 59901 | 43833 | 2.00 |
| Example 1 | 27183 | 52597 | 40326 | 1.93 |
| Example 2 | 33477 | 63263 | 47188 | 1.89 |
| Example 3 | 22667 | 38755 | 32730 | 1.71 |
| Example 4 | 24334 | 43463 | 35136 | 1.78 |
As can be seen from the test results in Table 1: the weight average molecular weight of the mother liquor of the polycarboxylate superplasticizer prepared in the comparative example 1 is 59901, the polydispersity is 2.00, and the molecular weight distribution is wide; the molecular weight polydispersity of examples 1-4 is less than 2.0, wherein the weight average molecular weight of example 3 is 38755, the polydispersity is only 1.71, and the molecular weight distribution is narrow. In conclusion, the chain transfer agent provided by the invention can better adjust the molecular weight of the polycarboxylate superplasticizer, and the molecular weight distribution of the polycarboxylate superplasticizer participating in synthesis is narrower.
In order to further verify the influence of the chain transfer agents of the examples 1 to 4 and the comparative example 1 on the mother liquor of the polycarboxylate superplasticizer, concrete experiments on the mother liquor of the polycarboxylate superplasticizer prepared in the examples 1 to 4 and the comparative example 1 are performed, and the concrete experimental materials are as follows:
cement: conch cement P.O 42.5.5; and (3) machining sand: machine-made sand produced locally in Guizhou, broken stone: crushed stone produced locally in Guizhou, water reducing agent: the mother liquors of the polycarboxylic acid water reducing agent prepared in examples 1 to 4 and comparative example 1 were diluted to 15% solids content.
The details of the machine-made sand used are shown in table 2 below:
TABLE 2 detailed information on machined Sand
| Appearance of the product | MB value | Fineness moduleFraction/%) | Apparent density kg/m3 | Source |
| White colour | 2.8 | 3.2 | 2490 | Local production in Guizhou |
The detailed information of the used gravels is shown in the following table 3:
TABLE 3 detailed gravel information
| Appearance of the product | Particle size/mm | MB value | Crush value/%) | Source |
| White colour | 5～35 | 1.2 | 12.6 | Local product of Guizhou province |
Concrete performance experiments are carried out according to the standard GB 8076-The concrete flow property and compressive strength of 5 samples were compared in C30 concrete test, wherein the concrete mixing ratio (unit: kg/m)3) As shown in table 4:
TABLE 4 concrete test mix proportions
| Sample name | Water (W) | Cement | Machine-made white sand | Crushing stone | Water reducing agent |
| Comparative example 1 | 165 | 340 | 1020 | 850 | 4.08 |
| Example 1 | 165 | 340 | 1020 | 850 | 4.08 |
| Example 2 | 165 | 340 | 1020 | 850 | 4.08 |
| Example 3 | 165 | 340 | 1020 | 850 | 4.08 |
| Example 4 | 165 | 340 | 1020 | 850 | 4.08 |
Concrete test evaluation is carried out according to the national standard GB/T50080-2016 common concrete mixture performance test method standard and detection is carried out according to GB 8076-2008 concrete admixture, and the measured data is shown in the following table 5:
TABLE 5 concrete Performance test
As can be seen from the test data in table 5:
in comparative example 1, the initial slump of the concrete was 210mm, the spread was 550mm, the slump after 2 hours was 185mm, and the spread was 380mm, and after 2 hours of the loss with time, the concrete spread was 170mm, and the loss with time of the spread was large;
in example 1, after 2h of time loss, the concrete expansion loss is 140 mm; in example 2, after 2h of time loss, the concrete expansion loss is 135 mm; in example 3, after 2h of time loss, the concrete expansion loss is 130 mm; in example 4, after 2h of time loss, the concrete expansion loss is 140 mm;
compared with the comparative example 1, the concrete in the examples 1 to 4 has smaller expansion loss with time, better slump retaining performance and improved slump retaining performance and compressive strength; the concrete in the embodiment 3 has initial expansion degree of 575mm, the expansion degree after 2h loss over time is 445mm, the concrete expansion degree loss is 130mm, the expansion degree loss over time is minimum, the slump retaining performance is good, the compressive strength is highest, and the concrete in the embodiment 3 has the best performance;
by combining the data analysis of tables 3 and 5, the polycarboxylic acid water reducing agent with wider molecular weight distribution provided in comparative example 1 has faster loss of the extension degree; the polycarboxylate superplasticizers with narrower molecular weight distributions provided in examples 1-4 have good initial flow property, better slump retaining property and higher compression resistance of concrete.
It should be noted that:
in addition to the practical choices embodied in the specific examples above, the aminobenzenesulfonate may be selected from: the general structural formula is as follows:
wherein M is Na+、K+，R1is-NH2、-CH2NH2、-CH2CH2NH2,R1The substitution position is-SO on the benzene ring3M is at least one of ortho, meta and para, the number of substitution is 1-3, including but not limited to the practical choices embodied in the above embodiments, specifically, the "number of substitution is 1-3" mentioned herein indicates that R is1The number of substituted positions is 1-3, and the substituted positions are represented by the following structural formula:
preferably, the aminobenzenesulfonate is one or more of sodium 4-aminobenzenesulfonate, potassium 4-aminobenzenesulfonate, sodium 2, 4-diaminobenzenesulfonate, potassium 2, 4-diaminobenzenesulfonate, sodium 4-aminomethyl benzenesulfonate, potassium 4-aminomethyl benzenesulfonate, sodium 2, 4-diaminomethylbenzenesulfonate and potassium 2, 4-diaminomethylbenzenesulfonate.
In addition to the practical choices embodied in the above specific examples, the choice of the functional thiol-based species may be: the general structural formula is as follows:
wherein R is2is-COOH, -SO3H, n is 2-3, including but not limited to the practical choices embodied in the above embodiments; preferably, the functional sulfydryl substance is one or more of thioglycolic acid, mercaptopropionic acid, 2-mercaptoethanesulfonic acid and 2-mercaptopropanesulfonic acid.
In addition to the practical choices embodied in the above specific examples, the catalyst is one or more combinations of metal chlorides and metal oxides, including but not limited to the practical choices embodied in the above examples; preferably, the catalyst is one or more of zinc oxide, zinc chloride, ferrous chloride and aluminum trichloride.
In addition to the actual selection embodied in the above specific embodiment, the reaction raw materials include 5-15 parts of aminobenzenesulfonate, 10-20 parts of functional mercapto substances and 0.01-0.1 part of catalyst; the raw material components in the above weight ratio range can all include, but are not limited to, the actual choices as shown in the above examples.
In addition to the actual selection of the synthetic process of the polycarboxylate superplasticizer embodied in the above specific embodiment, the synthetic method of the polycarboxylate superplasticizer is the prior art, and the regulation of the molecular weight of the polycarboxylate by adding the chain transfer agent in the synthetic reaction process of the polycarboxylate superplasticizer is also the prior art; therefore, based on the chain transfer agent for the polycarboxylate water reducer provided by the invention as the chain transfer agent, the specific selection of the specific preparation process parameters (reaction temperature, reaction time, and the like), the types of the polyether macromonomer and the unsaturated carboxylic acid, and the usage amount of the polyether macromonomer, the unsaturated carboxylic acid and the chain transfer agent in the synthesis process of the polycarboxylate water reducer can be adjusted in the field according to the above design concept, including but not limited to the scheme embodied in the embodiment.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (10)
1. A chain transfer agent for a polycarboxylate superplasticizer is characterized in that: the general structural formula is as follows:
wherein M is Na+Or K+The substitution position of R is-SO on the benzene ring3At least one of ortho position, meta position and para position of the M group has 1-3 substitution numbers, and the structural general formula of R is as follows:
wherein n is 2 to 3.
2. The chain transfer agent for a polycarboxylic acid water reducing agent according to claim 1, characterized in that: prepared by amidation reaction of aminobenzenesulfonate and functional sulfydryl substances under the catalysis of a catalyst;
5-15 parts of aminobenzenesulfonate, 10-20 parts of functional sulfydryl substances and 0.01-0.1 part of catalyst by weight.
3. The chain transfer agent for a polycarboxylic acid water reducing agent according to claim 2, characterized in that: the structural general formula of the aminobenzenesulfonate is as follows:
wherein M is Na+、K+，R1is-NH2、-CH2NH2、-CH2CH2NH2,R1The substitution position is-SO on the benzene ring3At least one of the ortho position, the meta position and the para position of M, and the number of substitution is 1-3.
4. The chain transfer agent for a polycarboxylic acid water reducing agent according to claim 2, characterized in that: the aminobenzenesulfonate is one or a combination of more of 4-aminobenzenesulfonic acid sodium, 4-aminobenzenesulfonic acid potassium, 2, 4-diaminobenzene sulfonic acid sodium, 2, 4-diaminobenzene sulfonic acid potassium, 4-aminomethyl benzene sulfonic acid sodium, 4-aminomethyl benzene sulfonic acid potassium, 2, 4-diaminomethyl benzene sulfonic acid sodium and 2, 4-diaminomethyl benzene sulfonic acid potassium.
5. The chain transfer agent for a polycarboxylic acid water reducing agent according to claim 2, characterized in that: the general structural formula of the functional sulfydryl substance is as follows:
wherein R is2is-COOH, -SO3H and n are 2-3.
6. The chain transfer agent for a polycarboxylic acid water reducing agent according to claim 2, characterized in that: the functional sulfydryl substance is one or a combination of more of thioglycolic acid, mercaptopropionic acid, 2-mercaptoethanesulfonic acid and 2-mercaptopropanesulfonic acid.
7. The chain transfer agent for a polycarboxylic acid water reducing agent according to claim 2, characterized in that: the catalyst is one or a combination of more of metal chloride and metal oxide.
8. Use of the chain transfer agent for a polycarboxylic acid water reducing agent according to any one of claims 1 to 7, characterized in that: the chain transfer agent is used as a chain transfer agent in the synthesis reaction of the polycarboxylic acid water reducing agent.
9. A method for preparing a chain transfer agent for a polycarboxylic acid water reducing agent according to any one of claims 1 to 7, characterized by comprising the steps of:
s100, adding aminobenzene sulfonate and a catalyst into a reaction kettle, stirring and mixing, and introducing inert gas to fill the reaction kettle until the amidation reaction is finished;
s200, heating the reaction temperature in the reaction kettle to 60-75 ℃, and adding a functional sulfydryl substance;
s300, after the functional sulfydryl substances are added, heating the reaction temperature to 85-105 ℃, and carrying out amidation reaction for a certain time at a constant temperature to obtain the chain transfer agent for the polycarboxylate superplasticizer.
10. The method for preparing a chain transfer agent for a polycarboxylic acid water reducer according to claim 9, characterized in that: in S200, slowly dripping the functional sulfydryl substances into a reaction kettle for 1-3 h; in S300, the amidation reaction time at constant temperature is 1-3 h.
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| US4005222A (en) * | 1975-05-21 | 1977-01-25 | Mead Johnson & Company | Mucolytic mercaptoacylamidobenzoic and benzenesulfonic acid compounds and process |
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| JPH09171252A (en) * | 1995-12-20 | 1997-06-30 | Fuji Photo Film Co Ltd | Radiation sensitive composition |
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