CN114149588A - Star initiator and preparation method thereof - Google Patents
Star initiator and preparation method thereof Download PDFInfo
- Publication number
- CN114149588A CN114149588A CN202111609180.XA CN202111609180A CN114149588A CN 114149588 A CN114149588 A CN 114149588A CN 202111609180 A CN202111609180 A CN 202111609180A CN 114149588 A CN114149588 A CN 114149588A
- Authority
- CN
- China
- Prior art keywords
- star
- initiator
- triethanolamine
- preparation
- core
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000003999 initiator Substances 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims abstract description 16
- YOCIJWAHRAJQFT-UHFFFAOYSA-N 2-bromo-2-methylpropanoyl bromide Chemical compound CC(C)(Br)C(Br)=O YOCIJWAHRAJQFT-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 7
- 238000007334 copolymerization reaction Methods 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims abstract 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 18
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 239000000706 filtrate Substances 0.000 claims description 6
- 238000003760 magnetic stirring Methods 0.000 claims description 6
- POPVULPQMGGUMJ-UHFFFAOYSA-N octasilsesquioxane cage Chemical compound O1[SiH](O[SiH](O2)O[SiH](O3)O4)O[SiH]4O[SiH]4O[SiH]1O[SiH]2O[SiH]3O4 POPVULPQMGGUMJ-UHFFFAOYSA-N 0.000 claims description 6
- 238000001291 vacuum drying Methods 0.000 claims description 6
- 238000004566 IR spectroscopy Methods 0.000 claims description 3
- 238000009833 condensation Methods 0.000 claims description 3
- 230000005494 condensation Effects 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 238000011049 filling Methods 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 239000002808 molecular sieve Substances 0.000 claims description 3
- 238000010992 reflux Methods 0.000 claims description 3
- 238000002390 rotary evaporation Methods 0.000 claims description 3
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 3
- -1 hydroxypropyl dimethylsilyl Chemical group 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 5
- 239000003638 chemical reducing agent Substances 0.000 abstract description 3
- 238000005917 acylation reaction Methods 0.000 abstract description 2
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 239000007788 liquid Substances 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 239000002699 waste material Substances 0.000 abstract description 2
- 239000002253 acid Substances 0.000 description 1
- 230000000740 bleeding effect Effects 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229920005646 polycarboxylate Polymers 0.000 description 1
- 230000000979 retarding effect Effects 0.000 description 1
- 239000008030 superplasticizer Substances 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
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/045—Polysiloxanes containing less than 25 silicon atoms
Abstract
The invention discloses a star-shaped initiator and a preparation method thereof, wherein the initiator takes triethanolamine as a core and is prepared by graft copolymerization reaction with 2-bromine-isobutyryl bromide by a core-arm-after-core method. Compared with the prior art, the invention has the advantages that: the invention discloses a novel star-shaped initiator prepared by starting from the synthesis of a star-shaped initiator on the basis of the accurate design of a molecular structure, adopting a route of 'nucleus' and 'arm' firstly, taking triethanolamine as a nucleus to perform acylation reaction with 2-bromo-isobutyryl bromide; the preparation method is simple, few in reaction steps, mild in reaction conditions, free of harmful waste liquid and environment-friendly; the star-shaped initiator has wide application prospect in the aspect of preparing high-performance water reducing agent.
Description
Technical Field
The invention relates to the technical field of initiators, in particular to a star initiator and a preparation method thereof.
Background
In recent decades, with the great progress of concrete preparation and construction technology at home and abroad, building structures with super high-rise, large span, high load and the like have made higher requirements on the strength, durability and the like of concrete. The concrete admixture is used as a fifth component indispensable to concrete besides cement, water, gravel aggregate and mineral admixture, and the corresponding demand for the concrete admixture is increasing. The polycarboxylic acid high-performance water reducing agent serving as the most common concrete admixture has the advantages of small mixing amount, high water reducing rate, good slump retaining performance, structural diversity and the like, and plays an important role in improving the fluidity and the workability of concrete, improving the compactness and the durability, controlling the problems of air entraining, retarding, bleeding and the like of the concrete. At present, researchers mainly focus on solving the problems of concrete dispersibility, dispersion retention and the like by preparing a comb-type polycarboxylate superplasticizer through molecular structure design, but the problems of single molecular structure, complex preparation process, high production cost and the like exist.
Disclosure of Invention
The invention aims to solve the technical problem of overcoming the technical defects and provides a star initiator and a preparation method thereof.
In order to solve the technical problems, the technical scheme provided by the invention is as follows: a star-shaped initiator is prepared from triethanolamine as core and 2-bromo-isobutyryl bromide through graft copolymerization.
A preparation method of a star initiator specifically comprises the following steps:
selecting a proper amount of triethanolamine, and drying by a molecular sieve;
step two, filling a proper amount of cage-type octasilsesquioxane into a three-mouth bottle with a condensation reflux device for magnetic stirring, adding anhydrous toluene into the bottle, adding allyl alcohol after the cage-type octasilsesquioxane is completely dissolved, heating, slowly adding a toluene solution after the temperature is raised to 50 ℃, and tracking the reaction process through infrared spectroscopy until a layered solution appears;
removing the upper-layer solution in the layered solution in the step two, concentrating the lower-layer solution, and drying to obtain hydroxypropyl dimethyl silicon alkyl cage POSS;
step four, adding the triethanolamine dried in the step one and the hydroxypropyl dimethyl silicon alkyl cage POSS obtained in the step three into a three-necked bottle for magnetic stirring, cooling the three-necked bottle to 0-3 ℃, adding 2-bromine-isobutyryl bromide into the three-necked bottle, reacting for 3-4 hours, and then extracting the filtrate;
and step five, carrying out rotary evaporation concentration on the filtrate extracted in the step four, and carrying out vacuum drying at room temperature for a certain time to obtain the star initiator.
Preferably, the molar ratio of the triethanolamine, the hydroxypropyl dimethylsilyl caged POSS and the 2-bromo-isobutyryl bromide in step four is 1:1: 1.1.
Preferably, the 2-bromo-isobutyryl bromide is added to the three-necked flask after the temperature of the three-necked flask in the fourth step is reduced to 0 ℃.
Preferably, the vacuum drying time in the fifth step is 24 h.
Compared with the prior art, the invention has the advantages that: the invention discloses a novel star-shaped initiator prepared by starting from the synthesis of a star-shaped initiator on the basis of the accurate design of a molecular structure, adopting a route of 'nucleus' and 'arm' firstly, taking triethanolamine as a nucleus to perform acylation reaction with 2-bromo-isobutyryl bromide; the preparation method is simple, few in reaction steps, mild in reaction conditions, free of harmful waste liquid and environment-friendly; the star-shaped initiator has wide application prospect in the aspect of preparing high-performance water reducing agent.
Detailed Description
A star-shaped initiator is prepared from triethanolamine as core and 2-bromo-isobutyryl bromide through graft copolymerization.
A preparation method of a star initiator specifically comprises the following steps:
selecting a proper amount of triethanolamine, and drying by a molecular sieve;
step two, filling a proper amount of cage-type octasilsesquioxane into a three-mouth bottle with a condensation reflux device for magnetic stirring, adding anhydrous toluene into the bottle, adding allyl alcohol after the cage-type octasilsesquioxane is completely dissolved, heating, slowly adding a toluene solution after the temperature is raised to 50 ℃, and tracking the reaction process through infrared spectroscopy until a layered solution appears;
removing the upper-layer solution in the layered solution in the step two, concentrating the lower-layer solution, and drying to obtain hydroxypropyl dimethyl silicon alkyl cage POSS;
step four, adding the triethanolamine dried in the step one and the hydroxypropyl dimethyl silicon alkyl cage POSS obtained in the step three into a three-necked bottle for magnetic stirring, cooling the three-necked bottle to 0-3 ℃, adding 2-bromine-isobutyryl bromide into the three-necked bottle, reacting for 3-4 hours, and then extracting the filtrate;
and step five, carrying out rotary evaporation concentration on the filtrate extracted in the step four, and carrying out vacuum drying at room temperature for a certain time to obtain the star initiator.
In the fourth step, the molar ratio of the triethanolamine, the hydroxypropyl dimethyl silyl cage POSS and the 2-bromo-isobutyryl bromide is 1:1: 1.1.
And step four, after the temperature of the three-necked bottle is reduced to 0 ℃, adding 2-bromine-isobutyryl bromide into the three-necked bottle.
And in the fifth step, the vacuum drying time is 24 hours.
The present invention and its embodiments have been described above, but the description is not limitative, and the actual structure is not limited thereto. In summary, those skilled in the art should appreciate that they can readily use the disclosed conception and specific embodiments as a basis for designing or modifying other structures for carrying out the same purposes of the present invention without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (5)
1. The star initiator is characterized in that triethanolamine is taken as a core, and the star initiator is prepared by graft copolymerization reaction of triethanolamine and 2-bromo-isobutyryl bromide by a core-arm-after-core method.
2. The method for preparing a star initiator according to claim 1, comprising the following steps:
selecting a proper amount of triethanolamine, and drying by a molecular sieve;
step two, filling a proper amount of cage-type octasilsesquioxane into a three-mouth bottle with a condensation reflux device for magnetic stirring, adding anhydrous toluene into the bottle, adding allyl alcohol after the cage-type octasilsesquioxane is completely dissolved, heating, slowly adding a toluene solution after the temperature is raised to 50 ℃, and tracking the reaction process through infrared spectroscopy until a layered solution appears;
removing the upper-layer solution in the layered solution in the step two, concentrating the lower-layer solution, and drying to obtain hydroxypropyl dimethyl silicon alkyl cage POSS;
step four, adding the triethanolamine dried in the step one and the hydroxypropyl dimethyl silicon alkyl cage POSS obtained in the step three into a three-necked bottle for magnetic stirring, cooling the three-necked bottle to 0-3 ℃, adding 2-bromine-isobutyryl bromide into the three-necked bottle, reacting for 3-4 hours, and then extracting the filtrate;
and step five, carrying out rotary evaporation concentration on the filtrate extracted in the step four, and carrying out vacuum drying at room temperature for a certain time to obtain the star initiator.
3. The star-shaped initiator and the preparation method thereof according to claim 2, wherein the molar ratio of the triethanolamine, the hydroxypropyl dimethylsilyl caged POSS and the 2-bromo-isobutyryl bromide in the fourth step is 1:1: 1.1.
4. The star-shaped initiator and the preparation method thereof according to claim 3, wherein the 2-bromo-isobutyryl bromide is added into the three-necked flask after the temperature of the three-necked flask in the fourth step is reduced to 0 ℃.
5. The star initiator and the preparation method thereof as claimed in claim 4, wherein the vacuum drying time in step five is 24 h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111609180.XA CN114149588A (en) | 2021-12-23 | 2021-12-23 | Star initiator and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111609180.XA CN114149588A (en) | 2021-12-23 | 2021-12-23 | Star initiator and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN114149588A true CN114149588A (en) | 2022-03-08 |
Family
ID=80451953
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111609180.XA Pending CN114149588A (en) | 2021-12-23 | 2021-12-23 | Star initiator and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114149588A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116178617A (en) * | 2022-10-25 | 2023-05-30 | 江苏超力建材科技有限公司 | Star-shaped high-performance polycarboxylate superplasticizer and preparation method thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101503497A (en) * | 2009-03-02 | 2009-08-12 | 江南大学 | Preparation of star type block acid sensitive nano micelle |
| US20140114030A1 (en) * | 2012-10-22 | 2014-04-24 | Beijing University Of Technology | Preparation method of high-performance star-shaped polycarboxylate superplasticizer |
| CN103910820A (en) * | 2014-03-31 | 2014-07-09 | 浙江工业大学 | Hexahedral silsesquioxane-based hyperbranched polymer and application of polymer in supercritical carbon dioxide foaming |
| CN104045778A (en) * | 2014-06-24 | 2014-09-17 | 南通茂林医用材料有限公司 | Preparation method of star-like hybrid material with UCST and polyhedral oligomeric silsesquioxane (POSS) as core |
| CN105271897A (en) * | 2015-11-25 | 2016-01-27 | 合肥工业大学 | Star-like polycarboxylate superplasticizer with high water-reducing rate and preparation method thereof |
| CN113773453A (en) * | 2021-09-22 | 2021-12-10 | 北方民族大学 | Hydrophilic chromatographic stationary phase for grafting copolymer brush on POSS silica gel, and preparation method and application thereof |
-
2021
- 2021-12-23 CN CN202111609180.XA patent/CN114149588A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101503497A (en) * | 2009-03-02 | 2009-08-12 | 江南大学 | Preparation of star type block acid sensitive nano micelle |
| US20140114030A1 (en) * | 2012-10-22 | 2014-04-24 | Beijing University Of Technology | Preparation method of high-performance star-shaped polycarboxylate superplasticizer |
| CN103910820A (en) * | 2014-03-31 | 2014-07-09 | 浙江工业大学 | Hexahedral silsesquioxane-based hyperbranched polymer and application of polymer in supercritical carbon dioxide foaming |
| CN104045778A (en) * | 2014-06-24 | 2014-09-17 | 南通茂林医用材料有限公司 | Preparation method of star-like hybrid material with UCST and polyhedral oligomeric silsesquioxane (POSS) as core |
| CN105271897A (en) * | 2015-11-25 | 2016-01-27 | 合肥工业大学 | Star-like polycarboxylate superplasticizer with high water-reducing rate and preparation method thereof |
| CN113773453A (en) * | 2021-09-22 | 2021-12-10 | 北方民族大学 | Hydrophilic chromatographic stationary phase for grafting copolymer brush on POSS silica gel, and preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| 张晓静等: ""一种星型聚合物引发剂的合成与表征"" * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116178617A (en) * | 2022-10-25 | 2023-05-30 | 江苏超力建材科技有限公司 | Star-shaped high-performance polycarboxylate superplasticizer and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105837763B (en) | Silane polycarboxylic acid water reducing agent and preparation method thereof | |
| WO2014085996A1 (en) | Slump retaining polycarboxylic acid superplasticizer | |
| CN107163201B (en) | The method that silane coupler modified polyethers prepares collapse protective poly-carboxylic acid water reducing agent | |
| CN108976355A (en) | A kind of polycarboxylate water-reducer and preparation method with high absorption property and low surface tension | |
| WO2022056975A1 (en) | Preparation method for polycarboxylic acid admixture for use in machine-made sand concrete | |
| CN114149588A (en) | Star initiator and preparation method thereof | |
| CN109437647B (en) | Polycarboxylic acid high-efficiency water reducing agent with enhanced adaptability and preparation method thereof | |
| CN101293757B (en) | Polyether modification type sulfamate water reducing agent and preparation method | |
| CN113149501A (en) | Internal curing material for ultra-high performance concrete and preparation method thereof | |
| CN109942754B (en) | Method for preparing delayed coagulation type superplasticizer by atom transfer radical polymerization | |
| CN108219080B (en) | Preparation method of polycarboxylate superplasticizer | |
| CN113444210B (en) | Low-sensitivity water-reducing slump-retaining polycarboxylic acid water reducer and preparation method thereof | |
| CN108484842B (en) | Ester low-sensitivity polycarboxylate superplasticizer and preparation method thereof | |
| CN114230727A (en) | Shrinkage-reducing ether polycarboxylate superplasticizer and preparation method thereof | |
| CN111808244B (en) | Polycarboxylate superplasticizer with high water reduction and high adaptability and preparation method thereof | |
| CN111620593B (en) | Anti-mud additive for reinforced concrete and preparation method thereof | |
| CN112608424B (en) | Ester ether copolymerization low-bleeding type polycarboxylate superplasticizer and preparation method thereof | |
| CN108706899B (en) | Preparation method of modified cement dispersant | |
| CN109762114B (en) | Early-strength viscosity-reduction type polycarboxylate superplasticizer containing double viscosity-reduction functional groups and preparation method thereof | |
| CN111087552A (en) | Synthetic method of polycarboxylic acid water reducer with high water reducing rate and mud resistance | |
| CN109336453A (en) | A kind of preparation method of nucleus type concrete super instant coagulant | |
| CN109776034B (en) | Application of viscosity-reducing water reducer containing alkyl in preparation of C100 concrete | |
| CN111978484A (en) | Silicon-containing magnetic polycarboxylate water reducer containing 4-hydroxybutyl polyoxyethylene ether | |
| CN112608425A (en) | Preparation method of water-reducing shrinkage-reducing agent | |
| CN101624270B (en) | High-efficiency polycarboxylic acid series water reducing agent and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20220308 |
|
| RJ01 | Rejection of invention patent application after publication |