CN104193215B - Ternary block macromonomer graft copolymerization high-property polycarboxylic acid water-reducing agent and preparation method thereof - Google Patents

Ternary block macromonomer graft copolymerization high-property polycarboxylic acid water-reducing agent and preparation method thereof Download PDF

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CN104193215B
CN104193215B CN201410442956.7A CN201410442956A CN104193215B CN 104193215 B CN104193215 B CN 104193215B CN 201410442956 A CN201410442956 A CN 201410442956A CN 104193215 B CN104193215 B CN 104193215B
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reducing agent
tri
water
block
graft copolymerization
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CN104193215A (en
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马保国
王允栋
黄健
谭洪波
方晨炜
戚长亚
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Wuhan University of Technology WUT
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Abstract

The invention discloses a ternary block macromonomer graft copolymerization high-property polycarboxylic acid water-reducing agent and a preparation method thereof. The preparation method comprises the following steps: dissolving a ternary block polyether macromonomer, a non-block polyether macromonomer and maleic anhydride into deionized water; then continuously stirring at a certain temperature, and respectively adding an initiating agent, a reducing agent and a chain transfer agent; and after the reaction is completed, regulating pH to neutrality to obtain the ternary copolymerization high-property polycarboxylic acid water-reducing agent. The water-reducing agent disclosed by the invention can enable the concrete to achieve higher flowing property under the condition of lower water cement ratio; because epoxy propane contained in the ternary block polyether macromonomer has an agglomeration effect and has high space steric effect, the synthesized polycarboxylic acid system water-reducing agent has more excellent dispersing retentivity, the water-reducing agent has lower air content when being used for the concrete, and the water-reducing agent is a multifunctional and high-adaptability high-property water-reducing agent which integrates water reduction, slump loss resistance and low air entrainment into a whole.

Description

A kind of tri-block polymeric monomer graft copolymerization high-performance polycarboxylic acids water reducing agent and preparation method thereof
Technical field
The present invention relates to a kind of tri-block polymeric monomer graft copolymerization high-performance polycarboxylic acids water reducing agent and preparation method thereof, belong to mixed Solidifying soil additive field.
Background technology
Along with modern science and technology and the development of production, the particularly proposition of " high performance concrete " this concept, concrete Use more focus on concrete durability, workability and adaptability in harsh use environment, this just requires water reducer There is certain bleed and good slump-retaining.Novel polycarboxylic acid concrete high efficiency water reducing agent must use point Sub-design principle, meets people and prepares low water binder ratio, high-strength, the demand of high durability concrete.There is comb shape molecule The polycarboxylic acid series high efficiency water reducing agent of structure is because its water-reducing rate is high, function of slump protection is good, volume is low, pollution-free, the slow setting time Less, the excellent properties such as low cost, the high-strength super high strength concrete of proper formulation, high fluidity and self-compacting concrete, become The focus of concrete admixture research and development both at home and abroad.
And the research of current domestic functional poly carboxylic acid water reducer is substantially blank, causes domestic water reducer mother solution product list One, and compound product is the most unstable, does not the most even reach anticipated effect, therefore, it is achieved water reducer functionalization sets Meter, the production of diversification mother solution, the popularization to polycarboxylate water-reducer has great importance.
The domestic people of there is presently no proposes the think of of synthesis of ternary block macromonomer graft copolymerization high-performance polycarboxylic acids water reducing agent synthesis Road.Particularly tri-block polyethers and isopentenol polyoxyethylene ether structure is simultaneously introduced, and does not also have at home in commercial production It has been proposed that.Chinese patent CN102911324A disclose a kind of method preparing maleic anhydride class polycarboxylate water-reducer and Purposes, it be with methyl allyl polyoxyethylene ether, containing sulfonate radical monomer and maleic anhydride as raw material, at Ammonium persulfate. be In the case of initiator, under 60-85 DEG C of reaction temperature, carry out reacting preparing for 4~7 hours, because it has the structure of side chain special Property, its molecule space steric hindrance increases, and the efficient based water reducer of polycarboxylic acids of synthesis has water-reducing rate height, protects the slow release that collapses, to environment The advantages such as close friend.But the structural particularity relying solely on polyethers side chain still can not make the efficient diminishing of polycarboxylic acids of synthesis Agent has best low air-entraining performance, protects the slow-releasing that collapses and had not the most reached optimal.
Chinese patent CN102503216A describes the synthetic method of a kind of universal polycarboxylic water reducer.This is general poly- Carboxylic acid water reducer is by modified polyoxyethylene ether or polyethenoxy ether and (methyl) acrylic acid or itaconic acid, metering system sulphur The universal polycarboxylic water reducer that the monomers such as acid sodium are prepared after being polymerized, cement mixture has high fluidity and high-thin arch dam Property and good workability, but this polycarboxylate water-reducer product bleed is poor, affects the intensity of concrete.
Chinese patent CN102951865A describes a kind of research work of air entrained type polycarboxylate high performance water-reducing agent and preparation method thereof. This air-entraining water-reducing agent is in aqueous medium, with methacrylic acid or acrylic acid as main chain, with unsaturated modified polyether Polymeric monomer (methyl thiazolinyl polyoxyethylene, allyl polyethenoxy ether or polyethenoxy ether) is research work of air entrained type prepared by side chain High-performance polycarboxylic acids water reducing agent.It is good that this water reducer has bleed performance, and the foaming size in introducing concrete is little, distribution is equal The characteristic that even, water-reducing rate is high, can improve the endurance quality of concrete, but the function of slump protection of this water reducer is bad, not Certain slow-releasing.
The purpose of the present invention is aiming at weak point and provides a kind of tri-block polymeric monomer graft copolymerization high-performance poly carboxylic acid diminishing Agent and preparation method thereof, preparation technology of the present invention is relatively easy, easy control of reaction conditions, and to producing, equipment requirements is relatively low, is A kind of low-dosage, water-reducing rate are high, function of slump protection is good, have the high-performance polycarboxylic acids water reducing agent of suitable bleed.
Summary of the invention
The technical problem to be solved is the deficiency existed for above-mentioned prior art and provides a kind of tri-block polymeric monomer Graft copolymerization high-performance polycarboxylic acids water reducing agent and preparation method thereof, is simultaneously introduced non-block and embedding in polycarboxylate water-reducer structure Section polyethers so that polycarboxylate water-reducer is ensureing while initial water-reducing rate height, has the slump retentivity of excellence, low Bleed.
A kind of tri-block polymeric monomer graft copolymerization high-performance polycarboxylic acids water reducing agent, its molecular weight ranges 15000~160000, knot Structure formula is shown below, wherein a:b:c=1:(0.15~0.3): (0.03~0.05), m is the integer of 58~125, m1、m3For The integer of 10~90;m2It it is the integer of 6~10.
By such scheme, described tri-block polymeric monomer graft copolymerization high-performance polycarboxylic acids water reducing agent is by maleic anhydride, tri-block Polyethers and isopentenol polyoxyethylene ether copolymerization form.
By such scheme, described tri-block polymeric monomer graft copolymerization high-performance polycarboxylic acids water reducing agent is at initiator, chain-transferring agent Effect, maleic anhydride, tri-block polyethers and isopentenol polyoxyethylene ether copolymerization in aqueous phase form, raw material composition join Ratio is by weight: maleic anhydride 5~15%, isopentenol polyoxyethylene ether 67.2~80%, tri-block polyethers 5~24%, Initiator 0.5~4%, chain-transferring agent 0.1~1%, reducing agent 0.05~1%.
The preparation method of above-mentioned tri-block polymeric monomer graft copolymerization high-performance polycarboxylic acids water reducing agent, specifically comprises the following steps that
1) by said ratio, prepare raw material maleic anhydride, isopentenol polyoxyethylene ether, tri-block polyethers, initiator and Chain-transferring agent, reducing agent;
2) maleic anhydride, isopentenol polyoxyethylene ether and tri-block polyethers are dissolved in suitable quantity of water, are warming up to 50~80 DEG C Stirring, adds initiator and drips the aqueous solution of chain-transferring agent and the aqueous solution of reducing agent respectively, and rate of addition is maintained at 0.25~0.5 ml/min, continues insulation reaction 20min~2h, is then cooled to room temperature, and regulates pH to 7~8 with aqueous slkali, I.e. obtain the finished product of tri-block polymeric monomer graft copolymerization high-performance polycarboxylic acids water reducing agent.
By such scheme, described tri-block polyethers is that a kind of epoxy ethane-epoxy propane-oxirane tri-block gathers Ether polymeric monomer (EPE), expoxy propane accounts for the 5~10% of tri-block polyether macromonomer gross mass, and molecular weight ranges is 2000~4500.
By such scheme, described isopentenol polyoxyethylene ether molecular weight ranges is 2600~5500.
By such scheme, described tri-block polyethers with the optimum weight ratio that feeds intake of isopentenol polyoxyethylene ether is 1:3.5~7.
By such scheme, described initiator is the one or two kinds of any of the above proportioning in Ammonium persulfate., potassium peroxydisulfate Mixture;More preferably one therein.
By such scheme, described reducing agent is the one or two kinds of any of the above proportioning in reducing sugar, ascorbic acid Mixture;More preferably one therein.
By such scheme, described chain-transferring agent is the one or two kinds of in TGA, mercaptopropionic acid, mercaptoethanol The mixture of any of the above proportioning;More preferably one therein.
By such scheme, described alkali is sodium hydroxide or potassium hydroxide aqueous solution, and mass concentration is advisable with 20~40%.
By such scheme, depending on the amount of water is according to practical situation in described step, generally make the grafting of tri-block polymeric monomer altogether The solid content of the finished product of poly-high-performance polycarboxylic acids water reducing agent is 10~50%.
By such scheme, described reducing agent and chain-transferring agent wiring solution-forming concentration are the aqueous solution of 0.3~5wt%.
The application process of tri-block polymeric monomer graft copolymerization high-performance polycarboxylic acids water reducing agent of the present invention: during use, will It, be spiked into the most in right amount in concrete, mix homogeneously with concrete according to common process.
The present invention selects isopentenol polyoxyethylene ether, tri-block polyethers EPE and maleic anhydride, and persulfate is as initiation Agent, prepares tri-block polymeric monomer graft copolymerization high-performance polycarboxylic acids water reducing agent.By unsaturated polymeric monomer, it is non-block especially Polyethers and block tri-block polyether macromonomer use simultaneously, are polymerized under the effect of initiator, make polymer introduce distinctive two Parent's property active group side chain, thus acquisition has, and water-reducing effect is excellent, function of slump protection is good, the high-performance poly carboxylic acid of low bleed effect Water reducer.In the present invention, the concrete equation of synthetic reaction is as follows:
Compared with prior art, the invention has the beneficial effects as follows:
(1) polycarboxylate water-reducer structure of the present invention introduces epoxy ethane-epoxy propane tri-block polyether macromonomer (EPE) so that polycarboxylate water-reducer has low air-entraining performance, the performance of cement water reducing agent is improved;It is simultaneously introduced non- Block, makes polycarboxylate water-reducer while ensureing initial water-reducing rate height with block polyether synergism, has excellence Slump retentivity;(2) preparation technology of the present invention is relatively easy, easy control of reaction conditions, to producing equipment requirements relatively Low, synthesized poly carboxylic acid series water reducer has more outstanding dispersion retentivity, low-dosage, water-reducing rate is high, have and suitably draw Gas.
Tri-block polymeric monomer graft copolymerization high-performance polycarboxylic acids water reducing agent of the present invention is possible not only to the bar at the relatively low ratio of mud Concrete can be made under part to reach higher mobile performance, again because the expoxy propane that block macromonomer is comprised has agglomerating effect, Having larger space steric effect, this makes synthesized poly carboxylic acid series water reducer have more outstanding dispersion retentivity, and this Water reducer for concrete time there is relatively low air content, be integrate diminishing, protect collapse and multi-functional, the adaptability of low bleed Strong high-performance water reducing agent.
Detailed description of the invention
For making those skilled in the art more clear and clear and definite technical scheme, the following preferred embodiment of special offer, but The technological thought of the present invention is not limited to following example.
Tri-block polymeric monomer graft copolymerization high-performance polycarboxylic acids water reducing agent of the present invention, its molecular weight ranges 15000~160000, general structure is shown below, wherein a:b:c=1:(0.15~0.3): (0.03~0.05), m is 58~125 Integer, m1、m3It it is the integer of 10~90;m2It it is the integer of 6~10.
Embodiment 1
The preparation method of above-mentioned tri-block polymeric monomer graft copolymerization high-performance polycarboxylic acids water reducing agent, specifically comprises the following steps that
The there-necked flask that will be equipped with agitator is positioned in control-temperature electric heating set, adds the prenol polyoxy that molecular weight is 2600 Vinyl Ether 155.1g, tri-block polyethers 27.4g, maleic anhydride 25.2g and water 200g, stir, be warming up to 75 DEG C; The most once add Ammonium persulfate. 7g, be simultaneously added dropwise Vitamin C aqueous acid 10.15g and (wherein contain ascorbic acid 0.15g), the aqueous solution 10.3g (wherein containing 0.3g TGA) of TGA, be added dropwise to complete after 4 hours (drip Acceleration is each about 0.4ml/min), continue insulation ripening 1 hour, add in the NaOH solution of 60g 30% and body It is pH to 7-8, i.e. obtains tri-block polymeric monomer graft copolymerization high-performance polycarboxylic acids water reducing agent.
The water reducer prepared by the present embodiment is diluted with water to the water reducer mother solution that solid content is 10%, is labeled as P1.
Wherein, the tri-block polyethers in the present embodiment is that epoxy ethane-epoxy propane-oxirane tri-block polyethers is big Monomer (EPE), expoxy propane accounts for the 10% of tri-block polyether macromonomer gross mass, and molecular weight is 2700.
Embodiment 2
The preparation method of above-mentioned tri-block polymeric monomer graft copolymerization high-performance polycarboxylic acids water reducing agent, specifically comprises the following steps that
The there-necked flask that will be equipped with agitator is positioned in control-temperature electric heating set, and adding molecular weight is 5500 prenol polyoxy second Alkene ether 146g, tri-block polyethers 36.5g, maleic anhydride 25.2g and water 200g, stir, be warming up to 75 DEG C;Then Once add Ammonium persulfate. 7g, be simultaneously added dropwise Vitamin C aqueous acid 10.15g (wherein containing ascorbic acid 0.15g), The aqueous solution 10.3g (wherein containing 0.3g TGA) of TGA, is added dropwise to complete after 4 hours that (rate of addition is equal It is about 0.4ml/min), continue insulation ripening 1 hour, add in the NaOH solution of 60g 30% and system pH to 6- 7, i.e. obtain tri-block polymeric monomer graft copolymerization high-performance polycarboxylic acids water reducing agent.
The water reducer prepared by the present embodiment is diluted with water to the water reducer mother solution that solid content is 10%, is labeled as P2.
Wherein, the tri-block polyethers in the present embodiment is that epoxy ethane-epoxy propane-oxirane tri-block polyethers is big Monomer (EPE), expoxy propane accounts for the 10% of tri-block polyether macromonomer gross mass, and molecular weight is 5600.
Embodiment 3
The preparation method of above-mentioned tri-block polymeric monomer graft copolymerization high-performance polycarboxylic acids water reducing agent, specifically comprises the following steps that
The there-necked flask that will be equipped with agitator is positioned in control-temperature electric heating set, and adding molecular weight is 2600 prenol polyoxy second Alkene ether 122.6g, tri-block polyethers 41.1g, maleic anhydride 25.2g and water 200g, stir, be warming up to 75 DEG C;So After once add Ammonium persulfate. 7g, be simultaneously added dropwise Vitamin C aqueous acid 10.15g and (wherein contain ascorbic acid 0.15g), the aqueous solution 10.3g (wherein containing 0.3g TGA) of TGA, be added dropwise to complete after 4 hours (drip Acceleration is each about 0.4ml/min), continue insulation ripening 1 hour, add in the NaOH solution of 60g 30% and body It is pH to 6-7, i.e. obtains tri-block polymeric monomer graft copolymerization high-performance polycarboxylic acids water reducing agent.
The water reducer prepared by the present embodiment is diluted with water to the water reducer mother solution that solid content is 10%, is labeled as P3.
Wherein, the tri-block polyethers in the present embodiment is that epoxy ethane-epoxy propane-oxirane tri-block polyethers is big Monomer (EPE), expoxy propane accounts for the 10% of tri-block polyether macromonomer gross mass, and molecular weight is 2700.
Comparative example
Comparative example 1: will be equipped with the there-necked flask of agitator and be positioned in control-temperature electric heating set, add molecular weight be 2600 different Pentenol polyoxyethylene ether 182.5g, maleic anhydride 25.2g and water 200g, be warming up to 75 DEG C, the most once after stirring Adding Ammonium persulfate. 7g, be simultaneously added dropwise ascorbic acid 0.15g and be dissolved in the reductant solution of 10g water, TGA 0.3g is molten In the chain-transferring agent solution of 10g water, drip 4 hours, insulation ripening 1 hour, add the NaOH solution of 60g30% Neutralization polymer, to pH=7-8, obtains polycarboxylate water-reducer.It is diluted with water to the water reducer mother solution of 10%, is designated as blank 1。
Comparative example 2: the polycarboxylate water-reducer KH-5 of the Wuhan Huaxuan High-tech Co., Ltd. bought on market is designated as Blank 2.
Application examples
Water reducer mother solution described in above-described embodiment and comparative example is respectively used in the production of commerical ready-mixed concrete, its preparation side Method is: proportioning raw materials is: cement: breeze: flyash: water: fluvial sand: rubble Water reducer volume described in=1.0:0.38:0.41:0.67:3.21:5.10, embodiment or comparative example is 0.2%.Concrete strength etc. Level is C40.The water-reducing rate of concrete, air content, the slump, divergence and comprcssive strength are all according to GB8076- In 2008 and GB50081-2002, associative operation is carried out, its testing result such as table 1.
Table 1
Test result: from concrete test interpretation of result, No. P1, No. P2 and No. P3 are in concrete bleed, diminishing effect Really aspect is better than comparative example 1 and comparative example 2, tri-block polymeric monomer graft copolymerization high-performance the most of the present invention Polycarboxylate water-reducer improves a lot than the effect of unblocked water reducer.Embodiment compares with blank example, implements Example is in the case of air content raising is more, it is ensured that the divergence of concrete, and makes the slump of concrete, intensity Corresponding improve, thus demonstrate tri-block of the present invention polymeric monomer graft copolymerization high-performance polycarboxylic acids water reducing agent institute table Reveal the excellent properties come.
The above is only the preferred embodiment of the present invention, it is noted that for the person of ordinary skill of the art, On the premise of conceiving without departing from the invention, it is also possible to making some modifications and variations, these broadly fall into the protection model of the present invention Enclose.

Claims (9)

1. a tri-block polymeric monomer graft copolymerization high-performance polycarboxylic acids water reducing agent, it is characterised in that its molecular weight ranges 15000~160000, general structure is as follows:
Wherein a:b:c=1:(0.15~0.3): (0.03~0.05), m is the integer of 58~125, m1、m3It it is the integer of 10~90;m2 It it is the integer of 6~10.
A kind of tri-block polymeric monomer graft copolymerization high-performance polycarboxylic acids water reducing agent the most according to claim 1, its feature It is that described tri-block polymeric monomer graft copolymerization high-performance polycarboxylic acids water reducing agent is by maleic anhydride, tri-block polyethers and iso-amylene Polyoxyethylenated alcohol copolymerization forms.
A kind of tri-block polymeric monomer graft copolymerization high-performance polycarboxylic acids water reducing agent the most according to claim 1, its feature It is that described tri-block polymeric monomer graft copolymerization high-performance polycarboxylic acids water reducing agent is in initiator, the effect of chain-transferring agent, by horse Coming anhydride, tri-block polyethers and isopentenol polyoxyethylene ether copolymerization in aqueous phase to form, raw material composition and ratio is by weight For: maleic anhydride 5~15%, isopentenol polyoxyethylene ether 67.2~80%, tri-block polyethers 5~24%, initiator 0.5~4%, chain-transferring agent 0.1~1%, reducing agent 0.05~1%.
4. according to a kind of tri-block polymeric monomer graft copolymerization high-performance polycarboxylic acids water reducing agent described in Claims 2 or 3, its The tri-block polyethers being characterised by described is a kind of epoxy ethane-epoxy propane-big list of oxirane tri-block polyethers Body, expoxy propane accounts for the 5~10% of tri-block polyether macromonomer gross mass, and molecular weight ranges is 2000~4500.
5. according to a kind of tri-block polymeric monomer graft copolymerization high-performance polycarboxylic acids water reducing agent described in Claims 2 or 3, its It is characterised by that its molecular weight ranges of described isopentenol polyoxyethylene ether is 2600~5500.
A kind of tri-block polymeric monomer graft copolymerization high-performance polycarboxylic acids water reducing agent the most according to claim 3, its feature It is the mixture that described initiator is the one or two kinds of any of the above proportioning in Ammonium persulfate., potassium peroxydisulfate.
A kind of tri-block polymeric monomer graft copolymerization high-performance polycarboxylic acids water reducing agent the most according to claim 3, its feature It is the mixture that described reducing agent is the one or two kinds of any of the above proportioning in reducing sugar, ascorbic acid.
A kind of tri-block polymeric monomer graft copolymerization high-performance polycarboxylic acids water reducing agent the most according to claim 3, its feature It is that described chain-transferring agent is the one or two kinds of any of the above proportioning in TGA, mercaptopropionic acid, mercaptoethanol Mixture.
The preparation side of a kind of tri-block polymeric monomer graft copolymerization high-performance polycarboxylic acids water reducing agent the most according to claim 3 Method, it is characterised in that specifically comprise the following steps that
1) by said ratio, prepare raw material maleic anhydride, isopentenol polyoxyethylene ether, tri-block polyethers, initiator and Chain-transferring agent, reducing agent;
2) maleic anhydride, isopentenol polyoxyethylene ether and tri-block polyethers are dissolved in suitable quantity of water, are warming up to 50~80 DEG C Stirring, adds initiator and drips the aqueous solution of chain-transferring agent and the aqueous solution of reducing agent respectively, and rate of addition is maintained at 0.25~0.5 ml/min, continues insulation reaction 20min~2h, is then cooled to room temperature, and regulates pH to 7~8 with aqueous slkali, I.e. obtain the finished product of tri-block polymeric monomer graft copolymerization high-performance polycarboxylic acids water reducing agent.
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