CN108822023A - Anti- mud agent of a kind of quaternary ammonium salt of amphoteric gemini containing bipyridyl and preparation method and application - Google Patents
Anti- mud agent of a kind of quaternary ammonium salt of amphoteric gemini containing bipyridyl and preparation method and application Download PDFInfo
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- CN108822023A CN108822023A CN201810679771.6A CN201810679771A CN108822023A CN 108822023 A CN108822023 A CN 108822023A CN 201810679771 A CN201810679771 A CN 201810679771A CN 108822023 A CN108822023 A CN 108822023A
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- China
- Prior art keywords
- mud
- bipyridyl
- agent
- preparation
- ammonium salt
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- 0 CC(CN*C=C1)=CC=C1c(cc1)cc*1[N+](O)[I-] Chemical compound CC(CN*C=C1)=CC=C1c(cc1)cc*1[N+](O)[I-] 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/06—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom
- C07D213/22—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom containing two or more pyridine rings directly linked together, e.g. bipyridyl
-
- 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
- C04B24/12—Nitrogen containing compounds organic derivatives of hydrazine
- C04B24/128—Heterocyclic nitrogen 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
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/0068—Ingredients with a function or property not provided for elsewhere in C04B2103/00
Abstract
A kind of preparation method of the anti-mud agent of the quaternary ammonium salt of amphoteric gemini containing bipyridyl, being structurally characterized in that for such anti-mud agent connect two symmetrical anion by quaternization reaction at the both ends of 4,4- bipyridyl, and the preparation method of the anti-mud agent is：With 4, 4- bipyridyl and sodium chloroacetate are raw material, after being dissolved in organic solvent, under conditions of 60-75 DEG C, it is prepared through quaternization reaction, the raw material that the preparation method of this kind of anti-mud agent is related to is cheap and easy to get, reaction condition is mild, synthesis step is simple, easy post-processing, it is compounded with polycarboxylic acids dehydragent and the anti-mud performance of cement can be improved, and there is good compatibility with polycarboxylate water-reducer, when montmorillonite content is 1%, anti- mud agent volume is 0.1 ‰, by itself and polycarboxylic acids water reducing agent compositional, the initial paste flowing degree of cement reaches 285mm, than improving 35mm before not compounding, flowing degree of net paste of cement is 270mm when 2h, loss late is 6.3%.The anti-mud time is long, and stability is good, and preparation process is simple, safety and environmental protection, is suitable for large-scale application.
Description
Technical field
The present invention relates to concrete admixture and technical field of surfactant, in particular to a kind of both sexes containing bipyridyl
Anti- mud agent of gemini quaternary ammonium salt and preparation method and application.
Background technique
Polycarboxylate dehydragent have high water reducing rate, high-thin arch dam, it is environmentally protective the advantages that, therefore in engineering concrete at
For essential external application additive.But it is sensitive to aggregate clay content, especially the soil in sandstone, and wherein sandstone includes natural
Sand and Machine-made Sand.In recent years, the exploitation due to people to natural sand stone causes good sandstone raw material exhausted, so turning machine
Sand processed.And Machine-made Sand corner angle are big, rough surface, clay content and mountain flour amount are high, are easier to the Free water and water-reducing agent of absorption system, lead
The just opposite reduction of the adsorbable effective water-reducing agent of cement institute and Free water is caused, very big influence is caused to its fluidity.Research hair
Montmorillonite in existing clay is maximum to the negative effect of water-reducing agent.The major measure taken at present has washing aggregate, but destroys bone
Expect structure, and is not easy to realize in construction；Secondly the water-reducing agent of excess is mixed, but will cause concrete water bleeding, isolates, collapses to it
Degree and intensity adversely affect；It is compounded also by anti-mud external application additive with water-reducing agent, reaches anti-mud effect.
Summary of the invention
In order to overcome the above-mentioned deficiencies of the prior art, the purpose of the present invention is to provide a kind of amphoteric geminis containing bipyridyl
Anti- mud agent of quaternary ammonium salt and preparation method and application has synthesis technology simple, and raw material is cheap and easy to get, is suitable for large-scale production
The characteristics of.
To achieve the goals above, the technical solution adopted by the present invention is that：
The anti-mud agent of a kind of quaternary ammonium salt of amphoteric gemini containing bipyridyl, by quaternization reaction, by two sodium chloroacetate monomers
The both ends for introducing 4,4- bipyridyl, with structure below：
A kind of preparation method of the anti-mud agent of the quaternary ammonium salt of amphoteric gemini containing bipyridyl, this method specifically include following steps：
Step 1：4,4- bipyridyl, sodium chloroacetate and organic are added in the three-necked flask equipped with stirring rod and condenser pipe
Solvent, heating carry out quaternization reaction and obtain mixed liquor I after reaction；
Step 2：Mixed liquor I is filtered to remove to extra organic solvent, obtains crude product II；
Step 3：The crude product II is mixed using ethyl acetate and is precipitated, filtered, dried the pyrrole containing connection can be obtained
The anti-mud agent of piperidinyl amphoteric gemini quaternary ammonium salt.
The molar ratio of 4,4- bipyridyl and sodium chloroacetate in the step 1 is 1:2~2.2, reaction raw materials with have
The mass ratio of solvent is 1:1~1.5.
Reaction temperature in the step 1 is 60~80 DEG C, and the reaction time is 7~10 hours.
Organic solvent in the step 1 include acetone, N,N-dimethylformamide, ethyl alcohol, tetrahydrofuran, in chloroform
Any one or two or more combinations；Preferably, the organic solvent is selected from acetone or n,N-Dimethylformamide.
The step 2 utilizes and is filtered to remove extra organic solvent.
In terms of a kind of anti-mud agent containing xenyl is applied to concrete external application additive, compound with water-reducing agent and improve anti-mud and imitate
Fruit.
Beneficial effects of the present invention：
1, the anti-mud agent of the quaternary ammonium salt of amphoteric gemini containing bipyridyl proposed is invented, synthesis technology is simple, and raw material is cheap
It is easy to get, reaction condition is mild, and well, environmentally protective and no pollution to the environment, yield is high, is suitable for large-scale production.
2, the anti-mud agent of the quaternary ammonium salt of amphoteric gemini containing bipyridyl proposed, compared with prior art, user are invented
Method is simple, with water-soluble, earth surfaces strong adsorption and stability it is good, and dosage is few, and using effect is good.It is covering
When de- soil content is 1%, anti-mud agent volume is 0.1 ‰, and by it, (rolling over solid volume is cement quality with polycarboxylate water-reducer
0.2%) it compounding, the initial paste flowing degree of cement reaches 285mm, than improving 35mm before not compounding, cement paste stream when 2h
Dynamic degree is 270mm, loss late 6.3%.The anti-mud time is long and stability is good, safety and environmental protection, is suitable for large-scale application.
Specific embodiment
Below with reference to embodiment, invention is further described in detail.
One, embodiment is prepared
Embodiment 1
(1) be added in the three-necked flask equipped with stirring rod and condenser pipe 15.6g4,4- bipyridyl (100mmol),
23.29g sodium chloroacetate (200mmol) and 48ml organic solvent ethyl alcohol are warming up to 60 DEG C, carry out 6 hours of quaternization reaction.
After reaction, mixed liquor I is obtained；
(2) mixed liquor I is obtained into crude product II using extra ethyl alcohol is filtered to remove；
(3) crude product II is precipitated using ethyl acetate, filtered, dry can be obtained it is a kind of containing bipyridyl
The anti-mud agent of amphoteric gemini quaternary ammonium salt, yield 76%.
Embodiment 2
(1) be added in the three-necked flask equipped with stirring rod and condenser pipe 15.6g4,4- bipyridyl (100mmol),
23.29g sodium chloroacetate (200mmol) and 48ml organic solvent-acetone are warming up to 70 DEG C, carry out 7 hours of quaternization reaction.
After reaction, mixed liquor I is obtained；
(2) mixed liquor I is obtained into crude product II using extra acetone is filtered to remove；
(3) crude product II is precipitated using ethyl acetate, filtered, dry can be obtained it is a kind of containing bipyridyl
The anti-mud agent of amphoteric gemini quaternary ammonium salt, yield 85%.
Embodiment 3
(1) be added in the three-necked flask equipped with stirring rod and condenser pipe 15.6g4,4- bipyridyl (100mmol),
25.52g sodium chloroacetate (220mmol) and 64ml organic solvent n,N-Dimethylformamide are warming up to 80 DEG C, carry out quaternized
React 8 hours.After reaction, mixed liquor I is obtained；
(2) mixed liquor I is obtained into crude product II using extra n,N-Dimethylformamide is filtered to remove；
(3) crude product II is precipitated using ethyl acetate, is filtered, dries novel amphoteric gemini season can be obtained
The anti-mud agent of ammonium salt, yield 87%.
Embodiment 4
(1) be added in the three-necked flask equipped with stirring rod and condenser pipe 15.6g4,4- bipyridyl (100mmol),
25.52g sodium chloroacetate (220mmol) and 64ml organic solvent n,N-Dimethylformamide are warming up to 75 DEG C, carry out quaternized
React 8 hours.After reaction, mixed liquor I is obtained；
(2) mixed liquor I is obtained into crude product II using extra n,N-Dimethylformamide is filtered to remove；
(3) crude product II is precipitated using ethyl acetate, filtered, dry can be obtained it is a kind of containing bipyridyl
The anti-mud agent of amphoteric gemini quaternary ammonium salt, yield 85%.
Current main additive is the anti-mud agent of small organic molecule, can be preferentially adsorbed in montmorillonite, its activity is occupied
Site is adsorbed on the water-reducing agent being added more on cement and reaches dispersion purpose.The anti-mud agent of small organic molecule mainly include yin from
Subtype and cationic and both sexes class.Due to being elecrtonegativity after montmorillonite water suction, and water-reducing agent is generally anionic, is added two
Property gemini quaternary ammonium salt cation can prevent native water swelling by electrostatic attraction strong adsorption in native surface and interlayer, shield it
To the Absorptive complex wave of water-reducing agent, and it can enter interlayer and reduce it to the absorption of water-reducing agent intercalation, weaken montmorillonite to the negative effect of slurry
It answers；And anion stretches to the outside of soil, adsorbable cement granules improve the dispersion performance of cement, improve paste flowing degree.
Based on the clay composition in montmorillonite simulation concrete, the present invention provides a kind of seasons of amphoteric gemini containing bipyridyl
Ammonium salt is as anti-mud agent, with polycarboxylic acids water reducing agent compositional later to the inhibitory effect of montmorillonite.Pass through the paste flowing degree of cement
Test, it is found that the anti-mud agent of the series has obviously effect.
Two, anti-mud effect
Novel gemini quaternary ammonium salt is compounded with the water-reducing agent that market is sold, gemini quaternary ammonium salt is same to mix respectively first to mix,
The mode mixed afterwards is compounded with polycarboxylate water-reducer, is tested by flowing degree of net paste of cement, as a result, it has been found that gemini quaternary ammonium salt with
The anti-mud effect that the mode and polycarboxylic acids water reducing agent compositional first mixed can perform better than.At room temperature, by testing cement paste stream
Dynamic degree carrys out paste flowing degree of the anti-mud agent prepared in embodiment 1,2,3,4 under 1% montmorillonite.It finds afterwards after tested：?
When montmorillonite content is 1%, anti-mud agent volume is 0.1 ‰, and by it, (rolling over solid volume is cement quality with polycarboxylate water-reducer
0.2%) it compounds, the initial paste flowing degree of cement is respectively 275mm, 270mm, 285mm, 270mm.The paste flowing degree of 2h is
260mm, 250mm, 275mm, 255mm, the anti-mud time is long and stability is good, and the anti-mud performance of embodiment 3 is best.In addition, through
When montmorillonite content increases, the anti-mud effect of such anti-mud agent is still good for test.Since reaction raw materials are cheap and easy to get, reaction
Mild condition, synthesis step is simple, easy post-processing, safety and environmental protection, is suitable for large-scale application.
Claims (7)
1. a kind of anti-mud agent of quaternary ammonium salt of amphoteric gemini containing bipyridyl, which is characterized in that by quaternization reaction, by two chloroethenes
Sour sodium monomer introduces the both ends of 4,4- bipyridyl, with structure below：
2. the preparation method based on anti-mud agent described in claim 1, which is characterized in that this method specifically includes following steps：
Step 1：4,4- bipyridyl, sodium chloroacetate and organic molten are added in the three-necked flask equipped with stirring rod and condenser pipe
Agent, heating carry out quaternization reaction and obtain mixed liquor I after reaction；
Step 2：By mixed liquor I using extra organic solvent is filtered to remove, crude product II is obtained；
Step 3：The crude product II is mixed using ethyl acetate and is precipitated, filtered, dried and can be obtained containing bipyridyl
The anti-mud agent of amphoteric gemini quaternary ammonium salt.
3. a kind of preparation method of anti-mud agent of the quaternary ammonium salt of amphoteric gemini containing bipyridyl according to claim 2, feature
It is, the molar ratio of 4,4- bipyridyl and sodium chloroacetate in the step 1 is 1:2~2.2, reaction raw materials with it is organic molten
The mass ratio of agent is 1:1~1.5.
4. a kind of preparation method of anti-mud agent of the quaternary ammonium salt of amphoteric gemini containing bipyridyl according to claim 2, feature
It is, the reaction temperature in the step 1 is 60~80 DEG C, and the reaction time is 7~10 hours.
5. a kind of preparation method of anti-mud agent of the quaternary ammonium salt of amphoteric gemini containing bipyridyl according to claim 2, feature
It is, the organic solvent in the step 1 includes acetone, n,N-Dimethylformamide, ethyl alcohol, tetrahydrofuran, appointing in chloroform
Meaning a combination of one or more；Preferably, the organic solvent is selected from acetone or n,N-Dimethylformamide.
6. a kind of preparation method of anti-mud agent of the quaternary ammonium salt of amphoteric gemini containing bipyridyl according to claim 2, feature
It is, the step 2 utilizes and is filtered to remove extra organic solvent.
In terms of 7. a kind of anti-mud agent containing xenyl according to claim 1 or 2 is applied to concrete external application additive, with
Water-reducing agent compounding improves anti-mud effect.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810679771.6A CN108822023A (en) | 2018-06-27 | 2018-06-27 | Anti- mud agent of a kind of quaternary ammonium salt of amphoteric gemini containing bipyridyl and preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810679771.6A CN108822023A (en) | 2018-06-27 | 2018-06-27 | Anti- mud agent of a kind of quaternary ammonium salt of amphoteric gemini containing bipyridyl and preparation method and application |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN108822023A true CN108822023A (en) | 2018-11-16 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810679771.6A Pending CN108822023A (en) | 2018-06-27 | 2018-06-27 | Anti- mud agent of a kind of quaternary ammonium salt of amphoteric gemini containing bipyridyl and preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108822023A (en) |
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2018
- 2018-06-27 CN CN201810679771.6A patent/CN108822023A/en active Pending
Non-Patent Citations (2)
| Title |
|---|
| 李军等: "吡啶季铵盐型中高温酸化缓蚀剂的合成与性能评价", 《石油化工应用》 * |
| 黎锦霞等: "季铵盐型抗泥剂的合成及其性能研究", 《广东建材》 * |
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Application publication date: 20181116 |