CN105271897A - Star-like polycarboxylate superplasticizer with high water-reducing rate and preparation method thereof - Google Patents
Star-like polycarboxylate superplasticizer with high water-reducing rate and preparation method thereof Download PDFInfo
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- CN105271897A CN105271897A CN201510844619.5A CN201510844619A CN105271897A CN 105271897 A CN105271897 A CN 105271897A CN 201510844619 A CN201510844619 A CN 201510844619A CN 105271897 A CN105271897 A CN 105271897A
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Abstract
The invention discloses a star-like polycarboxylate superplasticizer with high water-reducing rate and a preparation method thereof. The preparation method of the star-like polycarboxylate superplasticizer with high water-reducing rate is characterized by comprising the following steps: firstly carrying out acylation and bromination reactions on triethanolamine, so as to obtain a star-like initiator with a bromine terminal group; and then grafting hydroxyethyl methylacrylate to the star-like initiator, so that the star-like polycarboxylate superplasticizer with high water-reducing rate is obtained. The star-like polycarboxylate superplasticizer disclosed by the invention is high in water reducing rate, compressive strength of concrete can be improved, and higher construction requirements can be met.
Description
One, technical field
The present invention relates to a kind of preparation method of structure material, specifically a kind of preparation of hub-and-spoke configuration water reducer of high water reducing rate.
Two, background technology
Poly carboxylic acid series water reducer is a kind of polymeric surface active agent in essence, is mainly used in the mobility improving mixed territory, controls condensation or setting time, improves concrete strength etc.Poly carboxylic acid series water reducer has the excellent properties such as low-dosage, high water reducing rate, slow setting, low slump loss, production environmental protection.Poly carboxylic acid series water reducer great advantage is can by exchanging polymerization single polymerization monomer kind, change the product that the method design such as monomer proportioning and regulatory molecule amount goes out different molecular structures and performance, because of but a kind of structure design flexibility ratio is large, water reducer kind (the section Jianping that performance regulation and control space is large, Lv Shenghua. poly carboxylic acid series water reducer structure and dispersing property progress [J], mix territory .2011,11:59-66).This water reducer is except being applicable to normal concrete, also high-strength, the special concrete such as self-compacting, clear-water concrete of proper formulation, be widely used in key state project, especially traffic, hydro project etc. (Shi Caijun, what is rich and powerful, Liu Hui, Deng. the Recent Advances [J] of polycarboxylic acid series high efficiency water reducing agent, commerical ready-mixed concrete, 2010,2:20-23.; Xun Wuju, Wu Changlong etc. the status and prospectives [J] of polycarboxylic acid series high efficiency water reducing agent, contemporary chemical industry .2011,2:184-185.).
There is the poly carboxylic acid series water reducer of comb-type structure at present, be main chain with polyacrylic acid, main chain be grafted with sulfonic acid group (-SO
3h), hydroxy-acid group (-COOH) and polyoxyethylene group (-(CH
2cH
2o)-R) etc. side base and side chain.High-efficiency water-reducing agent of poly-carboxylic acid molecular backbone chain is connected with-C-C-key, and the adsorption groups such as molecular backbone chain base and sulfonic group can be adsorbed on cement particle surface, and forming one deck has certain thickness polymer adsorbed layers; Long side chain then can provide sterically hindered.When cement granules is close to each other, the sterically hindered effect provided by side chain can stop the close and reunion between cement granules, thus play disperse cement particles, improve the effect (Shou Chongqi of its mobility, Xu Lei. the hyperbranched star-like poly-greenbrier acid synthesis of water reducer and the application [J] in aluminosulfate cement thereof, New Building Materials .2011.12:18-23).
If sterically hindered larger group or segment are introduced polycarboxylic acid series high efficiency water reducing agent, or is introduced by water reducer in sterically hindered larger molecular structure, the water reducer that dispersion effect is more excellent may be obtained.
Three, summary of the invention
The present invention aims to provide poly carboxylic acid series water reducer of a kind of stelliform connection topology configuration and preparation method thereof, and technical problem to be solved selects suitable structure to improve the performance of poly carboxylic acid series water reducer by molecular designing.
Trolamine is a kind of branch's compound containing three hydroxyls.The present invention adopts star-like trolamine, 2 bromo-isobutyl acylbromides, hydroxyethyl methylacrylate to be raw material, with cuprous bromide, 2-2 dipyridyl for catalyst system, it is core that normal-temperature reaction obtains taking end group as the star-like initiator of bromine, the poly carboxylic acid series water reducer of the stelliform connection topology configuration with three knee-joint branches.Wherein the general structure of star-like polycarboxylate water-reducer is such as formula shown in (1), and the general structure of star-like initiator is such as formula shown in (2):
The preparation method of the star-like polycarboxylate water-reducer of the present invention is: first trolamine acyl bromination reaction, obtains the star-like initiator that end group is bromine; Then hydroxyethyl methylacrylate is received on described star-like initiator, namely obtain the star-like polycarboxylate water-reducer of high water reducing rate; Specifically comprise the following steps:
(1) trolamine acyl bromination reaction, obtains the star-like initiator that end group is bromine
Trolamine is dissolved in tetrahydrofuran (THF), and joins there-necked flask, and then the triethylamine added as acid binding agent and stirrer, in ice-water bath, stir half an hour under nitrogen atmosphere; The tetrahydrofuran solution of 2 bromo-isobutyl acylbromides is added drop-wise in described there-necked flask, stirring at room temperature reaction 24h under nitrogen atmosphere; By reaction solution suction filtration after reaction terminates, gained filtrate is placed in separating funnel, first washes with saturated sodium bicarbonate, then is neutralized to neutrality with deionized water; After washing, centrifugal removes tetrahydrofuran (THF), then is added drop-wise in ice ether and precipitates, and gained precipitation is the star-like initiator that end group is bromine; Reaction formula is as follows:
(2) hydroxyethyl methylacrylate is received on star-like initiator, obtain the star-like polycarboxylate water-reducer of high water reducing rate
Add in glass tube sealing after the star-like initiator dissolve with methanol that step (1) is obtained, then the monomers hydroxy ethyl ester adding 2-2 dipyridyl in glass tube sealing and be dissolved in the mixing solutions of deionized water and methyl alcohol, in liquid nitrogen, solid is frozen into remove oxygen after adding, add cuprous bromide and stirrer again, vacuumize, lead to nitrogen, stirring at room temperature reaction 12h; After reaction terminates, reaction solution is crossed neutral alumina pillar, after gained centrifugal removes solvent, joining cold tetrahydrofuran (THF) again (is still liquid, temperature is 0 DEG C-5 DEG C) in remove unreacted hydroxyethyl methylacrylate and star-like initiator, finally revolve tetrahydrofuran (THF), vacuum-drying, obtain the star-like polycarboxylate water-reducer of product.
Reaction formula is as follows:
Meet water due to 2 bromo-isobutyl acylbromides easily to react, each reactant in step (1) and solvent are all refining.Necessary anaerobic in step (2) grafting process, in order to avoid cuprous chloride is oxidized to cupric chloride.
In step (1), the mol ratio of trolamine, triethylamine and 2 bromo-isobutyl acylbromides is 1:3:3.3 ~ 4.The reaction mol ratio of trolamine TEA and 2 bromo-isobutyl acylbromides is 1:3, but meets water due to 2 bromo-isobutyl acylbromides and easily lose, and therefore its consumption should be slightly many.
In step (2), the mol ratio of star-like initiator, cuprous bromide, 2-2 dipyridyl and hydroxyethyl methylacrylate is 1:3:9:30 ~ 70.
The present invention utilizes the hydroxyl that trolamine 3 activity are higher, by itself and 2 bromo-isobutyl acylbromide acylbromides, thus 3 bromine end groups are introduced outside trolamine, then caused by it, with cuprous bromide, 2-2 dipyridyl for catalyst system, by the outside of hydroxyethyl methylacrylate monomer polymerization at initiator, obtain the poly carboxylic acid series water reducer of star topology.This topology configuration effectively can increase water reducer molecule and have stronger avidity to the adsorptive power of cement granules simultaneously, can the divergent function utilizing water reducer molecule of larger efficiency, flucculation structure between cement granules is destroyed, thus cement granules is fully disperseed.The product of this configuration can be arranged between cement granules fully, and the sterically hindered effect of more effective increase molecule, has oilness, and concrete mobility is strengthened.
Star-like water reducer refer to polyfunctional group organism be core, the class star-type polymer that is arm with poly carboxylic acid linear molecule, this base polymer has the character of star-like macromole and linear polymer molecule simultaneously, and star-type polymer can be combined with simple linear polymer.Due to the existence of terminal hydrophilic group and the structure of highly branched degree, star-type polymer synteny polymer phase ratio has good solvability; The limiting viscosity of star-type polymer molecule is more much lower than thread-like molecule, and this is that make intermolecular winding less, Intermolecular Forces is very little owing to containing a large amount of short-chain branchs in molecule; Star-type polymer has three-dimensional globular structure, and intermolecular without being wound around, and therefore the simple linear polymer of spatial volume comparatively with molecular weight is larger, plays stronger sterically hindered effect, and the water reducer of stelliform connection topology configuration of the present invention has higher adaptability and cement dispersiveness.
The present invention's star-like poly carboxylic acid series water reducer water-reducing rate is high, can improve concrete ultimate compression strength, meets higher construction requirement.
Four, accompanying drawing explanation
Fig. 1 is star-like initiator (TEA-Br
(3)), the infrared spectrum of trolamine (TEA) and 2 bromo-isobutyl acylbromides, as can be seen from Figure 1: c line is at 1807cm
-1the feature stretching vibration peak of the absorption peak C=O at place disappears; A line is at 1735cm
-1absorption peak be the stretching vibration peak of C=O in star-like initiator ester group; Trolamine acylbromide can be obtained thus and change into merit.
Fig. 2 is hydroxyethyl methylacrylate (HEMA), star-like poly carboxylic acid series water reducer (TEA-Br
(3)-PHEMA) and star-like initiator (TEA-Br
(3)) infrared spectrum, as can be seen from Figure 2: 1636cm on d line
-1for the C=C absorption peak of hydroxyethyl methylacrylate, and on e line, its peak disappears, and polymerization reaction take place is described; On e line, 3496cm
-1the new absorption peak produced in place is the feature stretching vibration peak of O-H; 1733cm on f line
-1place's absorption peak is the C=O peak in star-like initiator ester group; Successfully synthesized by the poly carboxylic acid series water reducer of the known stelliform connection topology configuration of upper analysis.
Fig. 3 is the paste flowing degree of the star-like polycarboxylate water-reducer of embodiment 1 gained, and time initial, degree of mobilization is the highest, and the time is longer, and degree of mobilization is less.
Fig. 4 is the paste flowing degree of the star-like polycarboxylate water-reducer of embodiment 2 gained, and time initial, degree of mobilization is the highest, and the time is longer, and degree of mobilization is less.
Fig. 5 is the paste flowing degree of the star-like polycarboxylate water-reducer of embodiment 3 gained, and time initial, degree of mobilization is the highest, and the time is longer, and degree of mobilization is less.
Five, embodiment
Embodiment 1:
The present embodiment prepares star-like polycarboxylate water-reducer as follows:
(1), the synthesis of star-like initiator (TEA-Br (3)):
3mmol trolamine is dissolved in 20mL purified tetrahydrofuran, and joins 50mL there-necked flask, and then add 9mmol as the triethylamine of acid binding agent and stirrer, under nitrogen atmosphere, in ice-water bath, stir half an hour; Be dissolved in 10mL tetrahydrofuran (THF) by 2 of 10mmol bromo-isobutyl acylbromides, then add in constant pressure funnel, regulate rate of addition to make it slowly be added drop-wise in there-necked flask, under dripping off rear nitrogen atmosphere, stirring at room temperature reacts 24h; By reaction solution suction filtration after reaction terminates, gained filtrate is placed in separating funnel, first washs three removing triethylamine salts with saturated sodium bicarbonate, then is neutralized to neutrality with deionized water; After washing, centrifugal removes tetrahydrofuran (THF), then is added drop-wise in ice ether and precipitates, and gained precipitation is the star-like initiator (TEA-Br (3)) that end group is bromine.
(2), polyreaction
Star-like initiator 0.12g (0.2mmol) step (1) obtained is with adding in glass tube sealing after a small amount of dissolve with methanol, then 2.34g (the 6mmol adding 0.2808g (1.8mmol) 2-2 dipyridyl in glass tube sealing and be dissolved in 20mL deionized water and methanol mixed solution (volume ratio 1:1), the ratio of initiator and hydroxyethyl methylacrylate is made to be 1:30) monomers hydroxy ethyl ester, in liquid nitrogen, solid is frozen into remove oxygen after adding, add 0.0861g (0.6mmol) cuprous bromide and stirrer again, repeatedly carry out vacuumizing logical nitrogen 3 times with three-way valve, stirring at room temperature reaction 12h, after reaction terminates, reaction solution is crossed neutral alumina pillar, gained centrifugal is removed after solvent, then joins in cold tetrahydrofuran (THF) and remove unreacted hydroxyethyl methylacrylate and star-like initiator, finally revolve tetrahydrofuran (THF), vacuum-drying, obtain the star-like polycarboxylate water-reducer of product.
With to roll over solid content be cement quality 0.2%, water cement ratio records the paste flowing degree of the star-like polycarboxylate water-reducer of the present embodiment gained for 293mm when being 0.29.
Embodiment 2:
The present embodiment prepares star-like polycarboxylate water-reducer by the mode that embodiment 1 is identical, and difference is only that the quality of hydroxyethyl methylacrylate in step (2) is 3.9g, and also namely the mol ratio of star-like initiator and hydroxyethyl methylacrylate is 1:50.
To roll over solid content is cement quality 0.2%, the paste flowing degree recording the present embodiment gained star-like polycarboxylate water-reducer when water cement ratio is 0.29 is 287mm.
Embodiment 3:
The present embodiment prepares star-like polycarboxylate water-reducer by the mode that embodiment 1 is identical, and difference is only that the quality of hydroxyethyl methylacrylate in step (2) is 5.46g, and also namely the mol ratio of star-like initiator and hydroxyethyl methylacrylate is 1:70.
With to roll over solid content be cement quality 0.2%, water cement ratio records the paste flowing degree of the star-like polycarboxylate water-reducer of the present embodiment gained for 303mm when being 0.29.
Claims (5)
1. a star-like polycarboxylate water-reducer for high water reducing rate, is characterized in that: the general structure of described star-like polycarboxylate water-reducer is such as formula shown in (1):
2. a preparation method for the star-like polycarboxylate water-reducer of high water reducing rate according to claim 1, is characterized in that: first trolamine acyl bromination reaction, obtains the star-like initiator that end group is bromine; Then hydroxyethyl methylacrylate is received on described star-like initiator, namely obtain the star-like polycarboxylate water-reducer of high water reducing rate;
The general structure of described star-like initiator is such as formula shown in (2):
3. preparation method according to claim 2, is characterized in that comprising the following steps:
(1) trolamine acyl bromination reaction, obtains the star-like initiator that end group is bromine
Trolamine is dissolved in tetrahydrofuran (THF), and joins there-necked flask, and then the triethylamine added as acid binding agent and stirrer, in ice-water bath, stir half an hour under nitrogen atmosphere; The tetrahydrofuran solution of 2 bromo-isobutyl acylbromides is added drop-wise in described there-necked flask, stirring at room temperature reaction 24h under nitrogen atmosphere; By reaction solution suction filtration after reaction terminates, gained filtrate is placed in separating funnel, first washes with saturated sodium bicarbonate, then is neutralized to neutrality with deionized water; After washing, centrifugal removes tetrahydrofuran (THF), then is added drop-wise in ice ether and precipitates, and gained precipitation is the star-like initiator that end group is bromine;
(2) hydroxyethyl methylacrylate is received on star-like initiator, obtain the star-like polycarboxylate water-reducer of high water reducing rate
Add in glass tube sealing after the star-like initiator dissolve with methanol that step (1) is obtained, then the monomers hydroxy ethyl ester adding 2-2 dipyridyl in glass tube sealing and be dissolved in the mixing solutions of deionized water and methyl alcohol, in liquid nitrogen, solid is frozen into remove oxygen after adding, add cuprous bromide and stirrer again, vacuumize, lead to nitrogen, stirring at room temperature reaction 12h; After reaction terminates, reaction solution is crossed neutral alumina pillar, gained centrifugal is removed after partial solvent, then joins in cold tetrahydrofuran (THF) and remove unreacted hydroxyethyl methylacrylate and star-like initiator, finally revolve tetrahydrofuran (THF), vacuum-drying, obtain the star-like polycarboxylate water-reducer of product.
4. preparation method according to claim 3, is characterized in that:
In step (1), the mol ratio of trolamine, triethylamine and 2 bromo-isobutyl acylbromides is 1:3:3.3 ~ 4.
5. preparation method according to claim 3, is characterized in that:
In step (2), the mol ratio of star-like initiator, cuprous bromide, 2-2 dipyridyl and hydroxyethyl methylacrylate is 1:3:9:30 ~ 70.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109134851A (en) * | 2018-09-04 | 2019-01-04 | 济南大学 | A kind of preparation and application of hyperbranched type water-reducing agent |
| CN114149588A (en) * | 2021-12-23 | 2022-03-08 | 江苏超力建材科技有限公司 | Star initiator and preparation method thereof |
| 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 (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101143916A (en) * | 2007-08-30 | 2008-03-19 | 复旦大学 | Method for preparing three hetero arms asteroid polymer |
| CN102002134A (en) * | 2010-11-05 | 2011-04-06 | 济南大学 | Hyperbranched polymer, hyperbranched type water reducing agent of polycarboxylic acid series and preparation method and application thereof |
| CN102775089A (en) * | 2012-08-21 | 2012-11-14 | 南京瑞迪高新技术有限公司 | Star polycarboxylic-acid high-performance water reducing agent and preparation method thereof |
| CN103333300A (en) * | 2013-06-27 | 2013-10-02 | 合肥工业大学 | Polycarboxylate-type water reducing agent with star topology and synthetical method thereof |
-
2015
- 2015-11-25 CN CN201510844619.5A patent/CN105271897B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101143916A (en) * | 2007-08-30 | 2008-03-19 | 复旦大学 | Method for preparing three hetero arms asteroid polymer |
| CN102002134A (en) * | 2010-11-05 | 2011-04-06 | 济南大学 | Hyperbranched polymer, hyperbranched type water reducing agent of polycarboxylic acid series and preparation method and application thereof |
| CN102775089A (en) * | 2012-08-21 | 2012-11-14 | 南京瑞迪高新技术有限公司 | Star polycarboxylic-acid high-performance water reducing agent and preparation method thereof |
| CN103333300A (en) * | 2013-06-27 | 2013-10-02 | 合肥工业大学 | Polycarboxylate-type water reducing agent with star topology and synthetical method thereof |
Non-Patent Citations (2)
| Title |
|---|
| 张晓静等: "一种星型聚合物引发剂的合成与表征", 《精细化工》 * |
| 程传杰等: "三臂ATRP引发剂的合成及应用", 《化学研究与应用》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109134851A (en) * | 2018-09-04 | 2019-01-04 | 济南大学 | A kind of preparation and application of hyperbranched type water-reducing agent |
| CN114149588A (en) * | 2021-12-23 | 2022-03-08 | 江苏超力建材科技有限公司 | Star initiator and preparation method thereof |
| 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 |
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