CN106748931B - A kind of star polycarboxylate water-reducer nucleating agent triethanolamine three（3- mercaptopropionic acids）Ester and preparation method thereof - Google Patents
A kind of star polycarboxylate water-reducer nucleating agent triethanolamine three（3- mercaptopropionic acids）Ester and preparation method thereof Download PDFInfo
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- CN106748931B CN106748931B CN201611032274.4A CN201611032274A CN106748931B CN 106748931 B CN106748931 B CN 106748931B CN 201611032274 A CN201611032274 A CN 201611032274A CN 106748931 B CN106748931 B CN 106748931B
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- triethanolamine
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- reducer
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- nucleating agent
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- 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
- C07C323/50—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 carboxyl groups bound to the same carbon skeleton
- C07C323/51—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 carboxyl groups bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton
- C07C323/52—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 carboxyl groups bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton the carbon skeleton being acyclic and saturated
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- 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
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- 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
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- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
A kind of preparation method of three (3 mercaptopropionic acid) ester of star polycarboxylate water-reducer nucleating agent triethanolamine includes the following steps:Nitrogen displacement is first carried out in the reactor with water knockout drum, is then added triethanolamine, and 3 mercapto-propionates, catalyst, azeotropic auxiliary agent stirs, heating, carries out reflux ester exchange reaction, catalyst secondary addition in four batches, whole nitrogen protection in reaction process；After reaction, vacuum distillation removes azeotropic auxiliary agent, obtains triethanolamine three (3 mercaptopropionic acid) ester；A kind of three (3 mercaptopropionic acid) ester of star polycarboxylate water-reducer nucleating agent triethanolamine of the present invention and preparation method thereof is with method is easy to operate, at low cost, raw material availability is high, (3 mercaptopropionic acid) ester conversion rate of gained triethanolamine three in terms of triethanolamine conversion up to 99%, purity is up to 99% or more, and impurity is less than 0.1%.
Description
Technical field
The invention belongs to high-molecular compound polymerization technique fields, and in particular to a kind of star polycarboxylate water-reducer nucleating agent
Triethanolamine three (3- mercaptopropionic acids) ester and preparation method thereof.
Background technology
Triethanolamine there are three the higher hydroxyl of reactivity and water-soluble amido, it can with much containing specific structure
Substance reaction, product are also equipped with water soluble characteristic, and the flexibility ratio of MOLECULE DESIGN is larger, and derivative object is the important building materials of a major class
Auxiliary agent intermediate, such compound can have more than two functional groups simultaneously, and it is early to be widely used in polycarboxylate water-reducer, concrete
The numerous areas of the building materials such as strong agent, cement grinding aid, macromolecule water-retaining agent, fungicide, coating additive, in recent years by domestic many
The extensive concern of more researchers.CN105523949A invents a kind of preparation side of acrylic acid triethanolamine esters compound
Method, the coupling agent that product can be used as cementing material use, and are widely used in resin industry.CN201080055967.X inventions one
Kind methacrylic acid and triethanolamine carry out esterification, the method for preparing methacrylic acid triethanolamine ester.
CN105461574A invents a kind of preparation method of triethanolamine oleate ester, which can be used for cutting fluid.CN102775438A
A kind of preparation method of triethanolamine phosphate ricinoleate compound is invented.The triethanolamine phosphate ricinoleate has excellent
Different wear-resistant and rustless property can meet the wear-resistant performance requirement with antirust of hydraulic fluid simultaneously.CN102911322B is with (methyl)
Acrylic acid and polyol reaction prepare the polymerizable active end of star by esterification under the action of catalyst, then with polymeric monomer,
Molecular weight regulator, unsaturated carboxylic acid monomer are made star polycarboxylic acids by Raolical polymerizable under the action of initiator and subtract
Aqua molecule.
Star structure molecule imparts many excellent performances of product and is widely noticed because of the particularity of its structure.Star
The research of polycarboxylate water-reducer is also the hot spot of water-reducing agent research.Product triethanolamine three (3- mercaptopropionic acids) ester of the present invention, tool
Standby three sulfydryls, the multi-functional chain-transferring agent that can be used as in polycarboxylate water-reducer synthesis use, to as star-shaped molecule at
Core agent will form three-arm star-shaped structural molecule using this product in the course of the polymerization process.
Invention content
First of the present invention is designed to provide a kind of three (3- sulfydryls of star polycarboxylate water-reducer nucleating agent triethanolamine
Propionic acid) ester.
Second object of the present invention is to provide above-mentioned three (3- sulfydryls of star polycarboxylate water-reducer nucleating agent triethanolamine
Propionic acid) ester preparation method.
The purpose of the present invention is what is realized by following technical measures：
A kind of three (3- mercaptopropionic acids) ester of star polycarboxylate water-reducer nucleating agent triethanolamine, it is characterised in that：Described three
The structural formula of ethanol amine three (3- mercaptopropionic acids) ester is expressed from the next：
A kind of preparation method of three (3- mercaptopropionic acids) ester of star polycarboxylate water-reducer nucleating agent triethanolamine, feature exist
In it includes the following steps:In the reactor with water knockout drum, nitrogen displacement is first carried out, triethanolamine is then sequentially added,
3- mercapto-propionates, catalyst, azeotropic auxiliary agent stir, and heating carries out reflux ester exchange reaction, advance in pipeline bottom
Purified water is added, to extract the methanol in azeotropic component, catalyst secondary addition in four batches, whole nitrogen protection in reaction process；
After reaction, vacuum distillation removes azeotropic auxiliary agent, obtains colourless transparent liquid triethanolamine three (3- mercaptopropionic acids) ester.
Further, the triethanolamine and 3- mercapto-propionates need to be 1 in molar ratio：3.5~4 feed intake.
Further, the catalyst is potassium carbonate, and dosage is the 5% of triethanolamine and 3- mercapto-propionate gross masses.
Further, the azeotropic auxiliary agent is hexamethylene, and dosage is triethanolamine and 3- mercapto-propionate gross masses
35%.
Further, it is 70 DEG C~90 DEG C that the reaction process, which need to be warming up to temperature,；Reaction time is 6 hours.
Further, the vacuum distillation temperature is 90 DEG C~105 DEG C；Vacuum degree is -0.09~-0.1Mpa；Time is
0.5 hour.
The present invention has following advantageous effect：
A kind of three (3- mercaptopropionic acids) ester of star polycarboxylate water-reducer nucleating agent triethanolamine of the present invention and preparation method thereof
It is easy to operate with method, at low cost, raw material availability is high, gained triethanolamine three (3- mercaptopropionic acids) ester conversion rate is with three second
Hydramine conversion meter up to 99%, purity is up to 99% or more, and impurity is less than 0.1%.Three (3- sulfydryls third of triethanolamine of the present invention
Acid) the multi-functional transfer agent that can be used as in polycarboxylate water-reducer synthesis of ester uses, and it will not shape as the nucleating agent of star-shaped molecule
At cross-linked polymer, molecular weight is three times of Conventional chain transfer agents, narrowly distributing, radial product high income.
Specific implementation mode
The present invention is specifically described below by embodiment, it is necessary to which indicated herein is that following embodiment is only used
In invention is further explained, it should not be understood as limiting the scope of the invention, without departing substantially from spirit of that invention
In the case of essence, to modifications or substitutions made by the method for the present invention, step or condition, all belong to the scope of the present invention.
Embodiment 1
In the reactor with water knockout drum, nitrogen displacement is first carried out, triethanolamine 149g, 3- mercapto is then sequentially added
Base methyl propionate 480g, partial catalyst potassium carbonate 7g, azeotropic auxiliary agent hexamethylene 220g, stirring heat up 80 DEG C, carry out reflux ester
Exchange reaction is previously added quantitative water in pipeline bottom, to extract the methanol in azeotropic component, every 1.5 hours of catalyst
7g is mended, adds up to four batches total 28g, whole process nitrogen protection in reaction process；When water phase quality increases 48g, reaction terminates.Decompression is steamed
Azeotropic auxiliary agent is removed in distillation, obtains colourless transparent liquid triethanolamine three (3- mercaptopropionic acids) ester, and conversion ratio is turned with triethanolamine
Change meter up to 99.3%, purity is up to 99.6%, impurity content 0.07%.
Embodiment 2
In the reactor with water knockout drum, nitrogen displacement is first carried out, triethanolamine 149g, 3- mercapto is then sequentially added
Base methyl propionate 420g, partial catalyst potassium carbonate 7g, azeotropic auxiliary agent hexamethylene 200g, stirring heat up 90 DEG C, carry out reflux ester
Exchange reaction is previously added quantitative water in pipeline bottom, to extract the methanol in azeotropic component, every 1.5 hours of catalyst
7g is mended, adds up to four batches total 28g, whole process nitrogen protection in reaction process；When water phase quality increases 48g, reaction terminates.Decompression is steamed
Azeotropic auxiliary agent is removed in distillation, obtains colourless transparent liquid triethanolamine three (3- mercaptopropionic acids) ester, and conversion ratio is converted with triethanolamine
Meter up to 99.1%, purity is up to 99.7%, impurity content 0.05%.
Embodiment 3
In the reactor with water knockout drum, nitrogen displacement is first carried out, triethanolamine 149g, 3- mercapto is then sequentially added
Base methyl propionate 456g, partial catalyst potassium carbonate 7g, azeotropic auxiliary agent hexamethylene 200g, stirring heat up 70 DEG C, carry out reflux ester
Exchange reaction is previously added quantitative water in pipeline bottom, to extract the methanol in azeotropic component, every 1.5 hours of catalyst
7g is mended, adds up to four batches total 28g, whole process nitrogen protection in reaction process；When water phase quality increases 48g, reaction terminates.Decompression is steamed
Azeotropic auxiliary agent is removed in distillation, obtains colourless transparent liquid triethanolamine three (3- mercaptopropionic acids) ester, and conversion ratio is converted with triethanolamine
Meter up to 99.5%, purity is up to 99.2%, impurity content 0.09%.
Claims (6)
1. a kind of preparation method of three (3- mercaptopropionic acids) ester of star polycarboxylate water-reducer nucleating agent triethanolamine, feature exist
In it includes the following steps:In the reactor with water knockout drum, nitrogen displacement is first carried out, triethanolamine is then sequentially added,
3- mercapto-propionates, catalyst, azeotropic auxiliary agent stir, and heating carries out reflux ester exchange reaction, advance in pipeline bottom
Purified water is added, to extract the methanol in azeotropic component, catalyst secondary addition in four batches, whole nitrogen protection in reaction process；
After reaction, vacuum distillation removes azeotropic auxiliary agent, obtains colourless transparent liquid triethanolamine three (3- mercaptopropionic acids) ester.
2. a kind of system of three (3- mercaptopropionic acids) ester of star polycarboxylate water-reducer nucleating agent triethanolamine as described in claim 1
Preparation Method, which is characterized in that the triethanolamine and 3- mercapto-propionates need to be 1 in molar ratio：3.5~4 feed intake.
3. a kind of three (3- mercaptopropionic acids) ester of star polycarboxylate water-reducer nucleating agent triethanolamine as claimed in claim 1 or 2
Preparation method, which is characterized in that the catalyst be potassium carbonate, dosage be triethanolamine and 3- mercapto-propionate gross masses
5%.
4. a kind of system of three (3- mercaptopropionic acids) ester of star polycarboxylate water-reducer nucleating agent triethanolamine as claimed in claim 3
Preparation Method, which is characterized in that the azeotropic auxiliary agent is hexamethylene, and dosage is triethanolamine and 3- mercapto-propionate gross masses
35%.
5. a kind of system of three (3- mercaptopropionic acids) ester of star polycarboxylate water-reducer nucleating agent triethanolamine as claimed in claim 4
Preparation Method, which is characterized in that it is 70 DEG C~90 DEG C that the reaction process, which need to be warming up to temperature, and the reaction time is 6 hours.
6. a kind of system of three (3- mercaptopropionic acids) ester of star polycarboxylate water-reducer nucleating agent triethanolamine as claimed in claim 5
Preparation Method, which is characterized in that the vacuum distillation temperature is 90 DEG C~105 DEG C, and vacuum degree is -0.09~-0.1Mpa, and the time is
0.5 hour.
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| CN201611032274.4A CN106748931B (en) | 2016-11-14 | 2016-11-14 | A kind of star polycarboxylate water-reducer nucleating agent triethanolamine three（3- mercaptopropionic acids）Ester and preparation method thereof |
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| CN201611032274.4A CN106748931B (en) | 2016-11-14 | 2016-11-14 | A kind of star polycarboxylate water-reducer nucleating agent triethanolamine three（3- mercaptopropionic acids）Ester and preparation method thereof |
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| Publication Number | Publication Date |
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| CN106748931A CN106748931A (en) | 2017-05-31 |
| CN106748931B true CN106748931B (en) | 2018-08-14 |
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| CN114775273B (en) * | 2022-04-13 | 2023-06-27 | 安徽弋尚纺织科技有限公司 | Pure cotton antibacterial fabric and processing technology thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5198131A (en) * | 1991-12-27 | 1993-03-30 | Mobil Oil Corporation | Dialkano- and trialkanol amine-derived thioester multifunctional antiwear additives |
| US5498686A (en) * | 1991-08-22 | 1996-03-12 | Optische Werke G. Rodenstock | Optically transparent photochromic plastic material |
| CN105026437A (en) * | 2013-02-15 | 2015-11-04 | 阿科玛法国公司 | Use of methyl mercapto-esters as chain transfer agents |
-
2016
- 2016-11-14 CN CN201611032274.4A patent/CN106748931B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5498686A (en) * | 1991-08-22 | 1996-03-12 | Optische Werke G. Rodenstock | Optically transparent photochromic plastic material |
| US5198131A (en) * | 1991-12-27 | 1993-03-30 | Mobil Oil Corporation | Dialkano- and trialkanol amine-derived thioester multifunctional antiwear additives |
| CN105026437A (en) * | 2013-02-15 | 2015-11-04 | 阿科玛法国公司 | Use of methyl mercapto-esters as chain transfer agents |
Non-Patent Citations (2)
| Title |
|---|
| 合成酯基锡化合物的新方法;田来进 等;《化学世界》;19951231;第493-494页 * |
| 碳酸钾催化酯交换合成碳酸二丁酯的研究;王庆印 等;《工业催化》;20050630;第13卷(第6期);第27-30页 * |
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