CN103965460A - Polycarboxylate-type water reducing agent - Google Patents
Polycarboxylate-type water reducing agent Download PDFInfo
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- CN103965460A CN103965460A CN201410213175.0A CN201410213175A CN103965460A CN 103965460 A CN103965460 A CN 103965460A CN 201410213175 A CN201410213175 A CN 201410213175A CN 103965460 A CN103965460 A CN 103965460A
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Abstract
The invention discloses a water reducing agent raw material, namely an ethylene oxide-propylene oxide ternary-block polyether macromonomer, as well as a water reducing agent prepared from the raw material. The preparation of the water reducing agent comprises the following processes: mixing iso-pentenol polyoxyethylene ether and a sodium alcoholate catalyst, heating to 80-115 DEG C and dealcoholizing; heating to 110-130 DEG C, controlling pressure to be 0.25-0.40Mpa and adding ethylene oxide; adding propylene oxide at unchanged system temperature and unchanged pressure; heating to 130-160 DEG C, controlling pressure to be 0.35-0.60Mpa, and adding ethylene oxide again; and after reaction, adding a weak acid neutralizer, thereby obtaining the ethylene oxide-propylene oxide ternary-block polyether macromonomer. Due to the use of a ternary-block system, the functional adjustment on a branched chain is easy to perform, and the adaptability and the slump loss resistance of a polycarboxylate-type water reducing agent monomer are enhanced greatly.
Description
Technical field
The invention belongs to building material technical field, be specifically related to the large monomer of a kind of water reducer raw material epoxy ethane-epoxy propane ternary block polyether, and the water reducer being prepared from.
Background technology
In recent years, the research of concrete admixture has tended to towards high-performance, pollution-free future development with production.Cement water reducing agent is a kind of that in concrete admixture, application surface is the widest, usage quantity is maximum.There is the polycarboxylic acid series high efficiency water reducing agent of comb shaped molecular structure because of excellent properties such as its water-reducing rate are high, function of slump protection is good, volume is low, pollution-free, the slow setting time is few, cost is low, the high-strength super high strength concrete of suitable preparation, high workability and self-compacting concrete, become the focus that domestic and international concrete admixture is researched and developed.The main direction of external current polycarboxylate water-reducer is multifunction, product seriation.Fast development along with concrete technology, admixture is proposed to some special requirements, as needed non-research work of air entrained type early strength water-reducing agent for shield pipe-plate, mass concrete needs slow setting and ultra-low hydration heat type water reducer, for hot summer, need low slump loss retarding water reducer, for needing early strong non-retarding water reducer etc. winter " singularity of the polytropy of environment, the diversity of concrete construction and Important Project, cement water reducing agent has been proposed to the requirement of functionalized design.Polycarboxylate water-reducer adopts aqueous free radical polymerization, and molecular structure degree of freedom is large, and capable of regulating side chain is realized the functionalized design of water reducer.And the research of current domestic functional poly carboxylic acid water reducer is blank substantially, cause domestic water reducer mother liquor product single, and composite product is often unstable, sometimes even do not reach the effect of expectation, therefore, realize the production of water reducer functionalized design, diversification mother liquor, the popularization of polycarboxylate water-reducer is had great importance.
Chinese patent CN101928392A discloses the preparation method of a kind of prenol Soxylat A 25-7 (TPEG), it take prenol and oxyethane is raw material, under the existence of catalyzer, under 70-160 ℃ of temperature of reaction, react and make for 5-40 hour, because it has the structure singularity of branched chain methyl, its molecule space steric hindrance increases, and the efficient based water reducer of synthetic poly carboxylic acid has that water-reducing rate is high, reinforced effects good, weather resistance, not Corrosion Reinforcement and the advantage such as environmentally friendly.It is sterically hindered or can not make synthetic high-efficiency water-reducing agent of poly-carboxylic acid have the dispersed hold facility of best cement granules that but the structure singularity that only relies on branched chain methyl provides.
Summary of the invention
The object of the invention is to develop the large monomer water reducer of a kind of new polyethers raw material, its can improve water reducer water-reducing rate, protect the performance of collapsing, also provide in addition and utilized the polycarboxylic acid series high efficiency water reducing agent that this large monomer is raw material.
The large monomer of epoxy ethane-epoxy propane ternary block polyether, adopt with the following method and prepare:
1) prenol Soxylat A 25-7 and sodium alkoxide catalyst mix are warming up to 80 ℃～115 ℃ dealcoholysis;
2) be warming up to 110 ℃～130 ℃ pressure and be controlled at 0.25～0.40Mpa, add oxyethane;
3) keep system temperature and the constant propylene oxide that adds of pressure;
4) continue to be warming up to 130 ℃～160 ℃ pressure and be controlled at 0.35～0.60Mpa, again add oxyethane, add after completion of the reaction weak acid neutralizing agent to obtain the large monomer of epoxy ethane-epoxy propane ternary block polyether;
Wherein, raw material is by massfraction, and described prenol Soxylat A 25-7 is 25～45%, alcohol sodium catalyst 0.2～0.6%, and the oxyethane adding for twice adds up to 65～80%, propylene oxide 15～35%, weak acid neutralizing agent 0.2～0.6%.
Press such scheme, be also included in after completion of the reaction and add weak acid neutralizing agent to carry out slaking insulation before, the temperature of described slaking insulation is controlled at 70 ℃～90 ℃, and the curing time is controlled at 0.5-1h.
Press such scheme, the molecular weight of described prenol Soxylat A 25-7 is 600～2000.
Press such scheme, described alcohol sodium catalyzer is sodium ethylate, sodium methylate or both mixtures.
Press such scheme, step 2) in step 4) in to add the mass ratio of oxyethane be 1-3:5.
More than one state the large monomer of epoxy ethane-epoxy propane ternary block polyether is the water reducer that raw material is prepared by autoreaction normal temperature synthetic technology.
In the synthetic water reducer of design polyether monomer used, add propylene oxide component, making resulting polyethers is the ternary system of epoxy ethane-epoxy propane-oxyethane.In water medium, on polyoxyethylene molecular chain, the hydrogen atom of Sauerstoffatom and water molecules forms hydrogen bond, and molecular chain is stretched, and has so just guaranteed the reactive behavior of pair keys in side chain.And that polyoxypropylene molecular chain is easily rolled up is folding, make hydrophobic methyl away from water molecules, increased like this steric effect.Therefore, it is larger sterically hindered that the side chain of the high-efficiency water-reducing agent of poly-carboxylic acid that this ternary system polyethers is synthetic can provide, thereby guarantee that cement granules disperses hold facility, and this is very useful to promoting workability and adaptability of polycarboxylic acid series high efficiency water reducing agent.
Beneficial effect of the present invention:
(1) adopt ternary block copolymer systems, the functionalization adjustment of side chain is easily carried out, greatly strengthened the adaptability of polycarboxylate water-reducer monomer.
(2) be different from traditional single ethylene oxide polymerization addition, adopted propylene oxide block addition, utilize polyoxypropylene chains under water surrounding, to roll up folding principle and increase steric effect, thereby strengthen the collapsing property of guarantor of water reducer, guarantee the dispersion retentivity of cement granules.
(3) adopt segmentation addition technology, can by the addition of second section propylene oxide, control the molecular weight of the polycarboxylic acid water reducer macromer of synthesized, also can control the length of polyoxyethylene chain, thereby regulate the performance of controlling large monomer.
Embodiment
Below in conjunction with specific examples, the present invention will be further described, but do not limit the scope of the invention.
The large monomer preparation process of epoxy ethane-epoxy propane ternary block polyether is as follows:
Batching: by massfraction, prenol Soxylat A 25-7 is 25～45%, alcohol sodium catalyst 0.2～0.6%, the oxyethane adding for twice adds up to 65～80%, propylene oxide 15～35%, weak acid neutralizing agent 0.2～0.6%.
1) prenol Soxylat A 25-7 and sodium alkoxide catalyst mix are warming up to 80 ℃～115 ℃ dealcoholysis;
2) be warming up to 110 ℃～130 ℃ pressure and be controlled at 0.25～0.40Mpa, add a part of oxyethane;
3) keep system temperature and the constant propylene oxide that adds of pressure;
4) continue to be warming up to 130 ℃～160 ℃ pressure and be controlled at 0.35～0.60Mpa, add remaining oxyethane, add after completion of the reaction weak acid neutralizing agent to obtain the large monomer of epoxy ethane-epoxy propane ternary block polyether;
Carrying out slaking insulation after completion of the reaction He before adding weak acid neutralizing agent, the temperature of described slaking insulation is controlled at 70 ℃～90 ℃, and the curing time is controlled at 0.5-1h.
Optimally, the molecular weight of prenol Soxylat A 25-7 is 600～2000.
Optimally, alcohol sodium catalyzer is sodium ethylate, sodium methylate or both mixtures.
Optimally, step 2) with step 4) in to add the mass ratio of oxyethane be 1-3:5.
Main purpose of the present invention is to take the large monomer of above-mentioned epoxy ethane-epoxy propane ternary block polyether by autoreaction normal temperature synthetic technology, to prepare the water reducer of excellent performance as raw material.
Embodiment 1: first with distilled water, the autoclave of 30L is rinsed well.After drying reactor, be cooled to room temperature, in reactor, adding molecular weight is 1000 prenol Soxylat A 25-7 6000g and 50g powdery sodium methylate, uses rare gas element N
2displace the air in reactor.Reactor temperature is promoted to 90 ℃ and carries out dealcoholization.Vacuum tightness in observing response still, starts to add 6000g oxyethane in vacuum in the situation that at reactor, this process keeps 130 ℃ of reactor temperatures, and flow control completed at 2 hours.Keep reactor temperature constant, continue to add 3600g propylene oxide in reactor, flow control completed at 1 hour.Rising temperature of reaction kettle to 145 ℃, joins remaining 14500g oxyethane in reactor, and flow control completed at 3.5 hours.Till insulation slaking to reacting kettle inner pressure no longer declines, approximately 1 hour.After complete reaction, be cooled to 75 ℃ and vacuumize after low boiling substance, add the neutralization of 60g acetic acid, last feeding packing.
This product is epoxy ethane-epoxy propane ternary block polyether monomer, and test data is: hydroxyl value 11.2, molecular weight 5017, iodine number 4.3.
Comparative example 1: first with distilled water, the autoclave of 30L is rinsed well.After drying reactor, be cooled to room temperature, in reactor, added prenol 720g and 54g powdery sodium methylate, used rare gas element N
2displace the air in reactor.Reactor temperature is promoted to 90 ℃ and carries out dealcoholization.Vacuum tightness in observing response still, starts to add 24500g oxyethane in vacuum in the situation that at reactor, this process keeps 130 ℃ of reactor temperatures, and flow control completed at 6 hours.Till insulation slaking to reacting kettle inner pressure no longer declines, approximately 2 hours.After complete reaction, be cooled to 75 ℃ and vacuumize after low boiling substance, add the neutralization of 50g acetic acid, last feeding packing.
This product is traditional oxyethane single-component polyether monomer, and test data is: hydroxyl value 11.0, molecular weight 5080, iodine number 4.3.
Embodiment 2: first with distilled water, the autoclave of 30L is rinsed well.After drying reactor, be cooled to room temperature, in reactor, adding molecular weight is 1000 prenol Soxylat A 25-7 6000g and 50g powdery sodium methylate, uses rare gas element N
2displace the air in reactor.Reactor temperature is promoted to 90 ℃ and carries out dealcoholization.Vacuum tightness in observing response still, starts to add 3120g oxyethane in vacuum in the situation that at reactor, this process keeps 130 ℃ of reactor temperatures, and flow control completed at 1.5 hours.Keep reactor temperature constant, continue to add 1875g propylene oxide in reactor, flow control completed at 1 hour.Rising temperature of reaction kettle to 145 ℃, joins remaining 7540g oxyethane in reactor, and flow control completed at 2.5 hours.Till insulation slaking to reacting kettle inner pressure no longer declines, approximately 1 hour.After complete reaction, be cooled to 75 ℃ and vacuumize after low boiling substance, add the neutralization of 35g acetic acid, last feeding packing.
This product is epoxy ethane-epoxy propane ternary block polyether monomer, and test data is: hydroxyl value 21.4, molecular weight 2620, iodine number 8.2.
Comparative example 2: first with distilled water, the autoclave of 30L is rinsed well.After drying reactor, be cooled to room temperature, in reactor, added prenol 240g and 20g powdery sodium methylate, used rare gas element N
2displace the air in reactor.Reactor temperature is promoted to 90 ℃ and carries out dealcoholization.Vacuum tightness in observing response still, starts to add 72500g oxyethane in vacuum in the situation that at reactor, this process keeps 130 ℃ of reactor temperatures, and flow control completed at 4.5 hours.Till insulation slaking to reacting kettle inner pressure no longer declines, approximately 1.5 hours.After complete reaction, be cooled to 75 ℃ and vacuumize after low boiling substance, add the neutralization of 32g acetic acid, last feeding packing.
This product is traditional oxyethane single-component polyether monomer, and test data is: hydroxyl value 21.5, molecular weight 2600, iodine number 8.2.
Employing is synthesized respectively water reducer mother liquor from the water-reducer at normal temperature production technology of heat release, autocatalysis by above-mentioned 4 kinds of polyether monomers.
The water reducer mother liquor of embodiment and comparative example polyether monomer synthesized is respectively used in the production of commerical ready-mixed concrete, its preparation method is: proportioning raw materials is: cement: breeze: flyash: water: river sand: rubble=1.0:0.38:0.41:0.67:3.21:5.10, synthetic water reducer volume is 0.15%.Strength grade of concrete is C40.
Cement used is the new P.O42.5 of China, and breeze is S95 level, and flyash is secondary ash, the medium sand that the fineness modulus of river sand is 2.7, and rubble is the stone of 5-31.5mm continuous grading.
Concrete water-reducing rate, air content, the slump, divergence and ultimate compression strength are all carried out according to relating operation in GB8076-2008 and GB50081-2002.
Its detected result is as shown in table 1.
Table 1
From concrete test interpretation of result, embodiment 1 and embodiment 2 disperse will be far superior to comparative example aspect retentivity at concrete, and the synthetic water reducer of the large monomer of epoxy ethane-epoxy propane ternary block polyether that namely the present invention produces is having very large lifting than traditional water reducer aspect collapsing property of guarantor.
Claims (6)
1. the large monomer of epoxy ethane-epoxy propane ternary block polyether, is characterized in that adopting with the following method and prepares:
1) prenol Soxylat A 25-7 and sodium alkoxide catalyst mix are warming up to 80 ℃～115 ℃ dealcoholysis;
2) be warming up to 110 ℃～130 ℃ pressure and be controlled at 0.25～0.40Mpa, add oxyethane;
3) keep system temperature and the constant propylene oxide that adds of pressure;
4) continue to be warming up to 130 ℃～160 ℃ pressure and be controlled at 0.35～0.60Mpa, again add oxyethane, add after completion of the reaction weak acid neutralizing agent to obtain the large monomer of epoxy ethane-epoxy propane ternary block polyether;
Wherein, raw material is by massfraction, and described prenol Soxylat A 25-7 is 25～45%, alcohol sodium catalyst 0.2～0.6%, and the oxyethane adding for twice adds up to 65～80%, propylene oxide 15～35%, weak acid neutralizing agent 0.2～0.6%.
2. the large monomer of epoxy ethane-epoxy propane ternary block polyether as claimed in claim 1, characterized by further comprising and carrying out slaking insulation after completion of the reaction He before adding weak acid neutralizing agent, the temperature of described slaking insulation is controlled at 70 ℃～90 ℃, and the curing time is controlled at 0.5-1h.
3. the large monomer of epoxy ethane-epoxy propane ternary block polyether as claimed in claim 1, is characterized in that the molecular weight of described prenol Soxylat A 25-7 is 600～2000.
4. the large monomer of epoxy ethane-epoxy propane ternary block polyether as claimed in claim 1, is characterized in that described alcohol sodium catalyzer is sodium ethylate, sodium methylate or both mixtures.
5. the large monomer of epoxy ethane-epoxy propane ternary block polyether as claimed in claim 1, is characterized in that step 2) in step 4) in to add the mass ratio of oxyethane be 1-3:5.
6. the large monomer of claim 1-5 any one epoxy ethane-epoxy propane ternary block polyether is the water reducer that raw material is prepared by autoreaction normal temperature synthetic technology.
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Cited By (10)
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| CN104193215A (en) * | 2014-09-02 | 2014-12-10 | 武汉理工大学 | Ternary block macromonomer graft copolymerization high-property polycarboxylic acid water-reducing agent and preparation method thereof |
| CN104860567A (en) * | 2015-05-12 | 2015-08-26 | 武汉理工大学 | Disperse thickening agent for phosphorus gypsum based self-leveling mortar and preparation method |
| CN107129571A (en) * | 2017-05-26 | 2017-09-05 | 浙江皇马科技股份有限公司 | A kind of prenol atactic polyether and preparation method thereof |
| CN107207678A (en) * | 2015-03-16 | 2017-09-26 | 可泰克斯公司 | It is used as the new copolymer of water reducer in hydraulic-composition |
| CN107265906A (en) * | 2017-06-15 | 2017-10-20 | 广东瑞安科技实业有限公司 | A kind of viscosity reduction type high performance water reducing agent of polyocarboxy acid and preparation method thereof |
| CN108003339A (en) * | 2017-12-26 | 2018-05-08 | 广东奥克化学有限公司 | A kind of block polyether for Early-strength polycarboxylate superplasticizer and preparation method thereof |
| CN108484897A (en) * | 2018-01-25 | 2018-09-04 | 北京砼帮汇科技有限公司 | A kind of polyoxy alkene ether monomer and the method for preparing polycarboxylate water-reducer with it |
| US10501371B2 (en) | 2015-03-16 | 2019-12-10 | Coatex | Copolymer as a water-reducing agent in a hydraulic composition and use of copolymers for improving the early mechanical strength of a hydraulic composition |
| CN112812289A (en) * | 2021-01-21 | 2021-05-18 | 吉林瑞吉特殊化学品有限公司 | Anti-mud ethoxylated naphthalene aromatic ring derivative monomer and preparation method thereof |
| CN114015034A (en) * | 2021-12-08 | 2022-02-08 | 江苏奥克化学有限公司 | Preparation method and application of sodium alkoxide catalyst for synthesizing water reducer polyether |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104193215B (en) * | 2014-09-02 | 2017-01-11 | 武汉理工大学 | Ternary block macromonomer graft copolymerization high-property polycarboxylic acid water-reducing agent and preparation method thereof |
| CN104193215A (en) * | 2014-09-02 | 2014-12-10 | 武汉理工大学 | Ternary block macromonomer graft copolymerization high-property polycarboxylic acid water-reducing agent and preparation method thereof |
| US10501371B2 (en) | 2015-03-16 | 2019-12-10 | Coatex | Copolymer as a water-reducing agent in a hydraulic composition and use of copolymers for improving the early mechanical strength of a hydraulic composition |
| CN107207678A (en) * | 2015-03-16 | 2017-09-26 | 可泰克斯公司 | It is used as the new copolymer of water reducer in hydraulic-composition |
| CN104860567A (en) * | 2015-05-12 | 2015-08-26 | 武汉理工大学 | Disperse thickening agent for phosphorus gypsum based self-leveling mortar and preparation method |
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| CN108003339A (en) * | 2017-12-26 | 2018-05-08 | 广东奥克化学有限公司 | A kind of block polyether for Early-strength polycarboxylate superplasticizer and preparation method thereof |
| CN108484897A (en) * | 2018-01-25 | 2018-09-04 | 北京砼帮汇科技有限公司 | A kind of polyoxy alkene ether monomer and the method for preparing polycarboxylate water-reducer with it |
| CN108484897B (en) * | 2018-01-25 | 2020-06-09 | 北京砼帮汇科技有限公司 | Polyoxyalkylene ether monomer and method for preparing polycarboxylate superplasticizer by using same |
| CN112812289A (en) * | 2021-01-21 | 2021-05-18 | 吉林瑞吉特殊化学品有限公司 | Anti-mud ethoxylated naphthalene aromatic ring derivative monomer and preparation method thereof |
| CN114015034A (en) * | 2021-12-08 | 2022-02-08 | 江苏奥克化学有限公司 | Preparation method and application of sodium alkoxide catalyst for synthesizing water reducer polyether |
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Application publication date: 20140806 |