CN103601881A - Functional polyether and method for preparing water reducer by using same - Google Patents
Functional polyether and method for preparing water reducer by using same Download PDFInfo
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Abstract
The invention discloses a preparation method of a functional polyether, and a method for preparing a polycarboxylic acid water reducer by using the functional polyether. The polyether is prepared by adding epoxyethane on the raw material 2,4,7,9-tetramethyl-5-decynyl-4,7-diol; and the production technique is simple and environment-friendly, is harmless to humans, animals and environment, and has the defoaming function. The water reducer is prepared by polymerizing the functional polyether to the molecular structure of the water reducer, so that the synthesized water reducer has the defoaming function and lowers the gas content in concrete; the minimum gas content in the synthesized water reducer is 1.7; and the water reducer endows the concrete with better operating performance, thereby being beneficial to the water reducing effect and maintenance effect of the water reducer.
Description
Technical field: the present invention relates to a kind of concrete admixture, be specifically related to the preparation method of the polyethers that synthesizing polycarboxylic acid dehydragent uses and use this polyethers to prepare the method for poly carboxylic acid series water reducer.
Background technology: polycarboxylate water-reducer when the concrete batching, has that low-dosage, dissemination are strong, little loss of slump, early strength strengthens and the characteristic such as good endurance.In addition, be also improved concrete hole structure and compaction rate, control better the function of the problems such as concrete bleed, slow setting, bleeding, become indispensable BSA in concrete mix.But many polycarboxylate dehydragent surfactivitys are high, guarantor's bubble property is good, and while being directly used in concrete, concrete 's air-containing is large, intensity is low, and therefore essential Compounded Antifoamer is used, to reduce concrete 's air-containing, raising concrete strength.The polycarboxylate water-reducer that defoamer is composite, the unnecessary air pocket in concrete that both disappeared, simultaneously owing to having reduced the air content in polycarboxylate water-reducer, has improved concrete hole structure and compaction rate, has improved concrete ultimate compression strength.But during Compounded Antifoamer, both can bring rolling up of allotment work, and along with the increase of defoamer volume, concrete through time loss also increase thereupon.Therefore, develop and the air content in concrete can be adjusted to suitable amount, and the polycarboxylate water-reducer that strengthens concrete strength has become the emphasis of research.
Not by composite, by synthetic method, solving the large problem of polycarboxylate concrete air content, is generally to introduce functional groups in polycarboxylate molecular structure, to regulate the HLB value of water reducer, improve its surface tension, this group of normal conditions has froth breaking characterization of molecules.The group of introducing can not have negative impact to concrete serviceability, can not be influential to the solvability of polycarboxylate water-reducer.2,4,7,9-tetramethyl--5-decine-4,7-glycol is a kind ofly to have wettingly, and froth breaking, improves dispersedly, can effectively reduce surface tension, control foam, the nonionic surface active agent of stable consistency and viscosity, but it is water-soluble low, can not be applied directly to the polymerization system of poly carboxylic acid series water reducer.Therefore, in addition after a small amount of oxyethane, improved that it is water-soluble, synthetic polyethers itself also still has their defoaming function, directly apply to polymerization system, make synthetic water reducer itself also there is the bubble of control function, further improved the performance of poly carboxylic acid series water reducer.
Summary of the invention:
Goal of the invention: the object of this invention is to provide a kind of preparation method of functional polyethers and the method for the poly carboxylic acid series water reducer prepared with this polyethers, to obtain steady quality, function of slump protection is good, water-reducing rate is high, good with the adaptability of other concrete admixtures, the advantages such as environmental protection, the most importantly suitable water reducer of air content.
Technical scheme: the present invention implements by the following technical programs:
A functionalised polyethers, is characterized in that: this polyethers is with oxyethane and 2,4,7,9-tetramethyl--5-decine-4, and 7-glycol is raw material, under following reaction conditions, reacts:
A) polyethers is by oxyethane and 2,4,7,9-tetramethyl--5-decine-4,7-glycol reacts under catalyst action, and temperature of reaction is 80-120 ℃, and reaction pressure is 0.1-0.4MPa, and 2,4,7,9-tetramethyl--5-decine-4, the mole ratio of 7-glycol and oxyethane is 1:1-4;
B) used catalyst is one or more mixing in sodium hydroxide, potassium hydroxide, sodium cyanide, and catalyst levels is the 0.005-0.2% of reactant total mass, and the synthetic polyethers of described method is TMDEG, has following structure:
Wherein, the real number that n is 1-4.
This polyethers is applied in polycarboxylic acid series, and under the condition being existed at initiator by each comonomer, copolyreaction in the solvent stirring and obtaining, is specially:
Described comonomer is to consist of component A and B component, and the quality of component A accounts for the 60-90% of monomer total mass, and all the other are B component, wherein,
Component A: be the mixture of component A1 and component A2, A1 is selected from the polyether monomer that molecular weight is 400-4000, is selected from one or more mixing in propylene alcohol ether, methacrylic alcohol ether, butylene alcohol ether, methyl butene alcohol ether; Component A2 is TMDEG;
B component: B component is selected from one or more mixing in methacrylic acid, vinylformic acid, toxilic acid, maleic anhydride, Hydroxyethyl acrylate, Propylene glycol monoacrylate, acrylamido-methyl propane sulfonic acid, methylpropene sodium sulfonate;
Described solvent is water; Described polymeric reaction temperature is 50-90 ℃, and the reaction times is 3-8 hour;
After polyreaction completes, in copolymerization product, add sodium hydroxide solution neutralization, regulate pH value at 6-7.
The initiator that described copolyreaction adopts consists of Oxidizing and Reducing Agents, and wherein oxygenant is selected from one or more mixing in Sodium Persulfate, ammonium persulphate, Potassium Persulphate or hydrogen peroxide; Reductive agent is selected from one or more mixing in xitix, sodium bisulfite, glucose, rongalite, and in reaction system, the total mass of redox agent is the 1-8% of monomer total mass.
Advantage and effect: 1, the production technique of polyethers is simple, and raw material is easily purchased; Temperature of reaction and pressure are all lower, operational safety; Synthetic polyethers is harmless to humans and animals, environmental sound, environmental protection;
2, the present invention introduces a kind of polyethers TMDEG with their defoaming function in polycarboxylate water-reducer technique, the introducing of TMDEG makes the surface tension of water reducer itself low, so the concrete 's air-containing of preparation is also low especially, air content can, lower than 3%, be suitable for high-strength, super high strength concrete.Given concrete better serviceability;
3, this froth breaking polyethers participates in polymerization, has changed polycarboxylate water-reducer molecular structure, has changed the density of side chain on unit length chain link, is conducive to water reducer molecule and slowly discharges in concrete, is conducive to the water-reducing effect of water reducer and keeps effect.
4, water reducer of the present invention has directly been introduced froth breaking polyethers in molecule, has increased the consistency of water reducer and other concrete admixtures, is conducive to a large amount of uses of poly carboxylic acid series water reducer in concrete;
5, the polyether monomer in water reducer of the present invention is not limited to kind.The polyether monomer of energy polymerization can directly be introduced TMDEG;
6, water reducer of the present invention has introduced defoamer in polymerization, and later stage and other compounding concrete admixtures need not add defoamer while using again, so do not increase on cost;
7, in polymerization, be directly to quote defoamer, improved the viscosity of concrete mortar, improved concrete workability;
8, improved the dispersiveness between traditional defoamer and admixture, reached the shelf-time on result the effect without impact.
Embodiment: the invention will be further described below in conjunction with example:
The present invention relates to two steps, the one, the preparation of this kind of functionalised polyethers, the 2nd, the preparation of the poly carboxylic acid series water reducer that comprises this polyether monomer.The preparation of described polyethers is that 7-glycol is raw material, under following reaction conditions, reacts with oxyethane and 2,4,7,9-tetramethyl--5-decine-4:
A) polyethers is by oxyethane and 2,4,7,9-tetramethyl--5-decine-4,7-glycol reacts under catalyst action, and temperature of reaction is 80-120 ℃, and reaction pressure is 0.1-0.4MPa, and 2,4,7,9-tetramethyl--5-decine-4, the mole ratio of 7-glycol and oxyethane is 1:1-4.
B) used catalyst is one or more mixing in sodium hydroxide, potassium hydroxide, sodium cyanide, and catalyst levels is the 0.005-0.2% of reactant total mass.
In technique scheme, the temperature of reaction of reaction process condition is preferably 90-110 ℃; Reaction pressure is preferably 0.3-0.4MPa; Catalyst levels is preferably 0.15-0.2%.Synthetic polyethers has following structure:
Wherein, the real number that n is 1-4.
TMDEG prepared by the present invention is a kind of solvability defoamer, in the extremely low situation of polymerization volume, just can reduce the air content of poly carboxylic acid series water reducer, improves workability.Under the condition that the preparation of water reducer is existed at initiator by each copolymerization monomer, stir and in solvent, carry out copolyreaction and obtain:
Described comonomer is to consist of component A and B component, and the quality of component A accounts for the 60-90% of monomer total mass, wherein,
Component A: be the mixture of component A1 and component A2, wherein A1 is selected from the polyether monomer that molecular weight is 400-4000, is selected from one or more mixing in propylene alcohol ether, methacrylic alcohol ether, butylene alcohol ether, methyl butene alcohol ether; Component A2 is TMDEG;
B component: B component is selected from one or more mixing in methacrylic acid, vinylformic acid, toxilic acid, maleic anhydride, Hydroxyethyl acrylate, Propylene glycol monoacrylate, acrylamido-methyl propane sulfonic acid, methylpropene sodium sulfonate;
Described solvent is water; Described polymeric reaction temperature is 50-90 ℃, and the time is 3-8 hour;
After polyreaction completes, in copolymerization product, add sodium hydroxide solution neutralization, regulate pH value at 6-7.Preferred technical scheme, the initiation method that described copolyreaction adopts is redox system, and initiator consists of Oxidizing and Reducing Agents, and wherein oxygenant is selected from a kind of in Sodium Persulfate, ammonium persulphate, Potassium Persulphate or hydrogen peroxide; Reductive agent is selected from one or more mixing in xitix, sodium bisulfite, glucose, rongalite, and according to the kind of oxygenant, can select to add and not add,, in reaction system, the total mass of redox initiator is the 1-8% of monomer total mass.
In technique scheme, the feed way of component A, for to add together with solvent in reactor, is warming up to component A and all dissolves.Preferred technical scheme, the concentration of described component A1 in solvent is 60-70%, the concentration of component A2 in solvent is 0.1%.
In technique scheme, the feed way of B component and initiator, for being added drop-wise in reactor, first drips initiator solution when the aqueous solution of A material is warmed up to temperature of reaction, drips B component solution after 2min clock.
In order to simplify statement, below with AL, represent " propylene alcohol ether "; With MAL, represent " methacrylic alcohol ether "; With BL, represent " butylene alcohol ether "; With MBL, represent " methyl butene alcohol ether "; With TMDD, represent " ethoxylation 2,4,7,9-tetramethyl--5-decine-4,7-glycol ", with TMDEG, represent " ethoxylation 2,4,7,9-tetramethyl--5-decine-4,7-glycol ethers "; With MA, represent " maleic anhydride "; With AA, represent " vinylformic acid "; With APS, represent " ammonium persulphate ".
Embodiment mono-:
First in reactor, pass into 67.8 grams of TMDD, add the sodium hydroxide of 0.162 gram, with after N2 displacement, reactor heats up, and starts to pass into oxyethane when reactor is warming up to 80 ℃ in reactor, and add-on is 13.2 grams.Control reaction pressure and be less than 0.4MPa, 100 ℃-110 ℃ of temperature of reaction are carried out polyreaction, after treating that oxyethane all adds, are incubated aging 30min.Agingly be cooled to 70 ℃ after complete, with Glacial acetic acid, be neutralized to pH value 6～7, discharging.Note is TMDEG-1.
Embodiment bis-:
First in reactor, pass into 67.8 grams of TMDD, add the sodium hydroxide of 0.2201 gram, with after N2 displacement, reactor heats up, and starts to pass into oxyethane when reactor is warming up to 80 ℃ in reactor, and add-on is 42.24 grams.Control reaction pressure and be less than 0.4Mpa, 100 ℃-110 ℃ of temperature of reaction are carried out polyreaction, after treating that oxyethane all adds, are incubated aging 30min.Agingly be cooled to 70 ℃ after complete, with Glacial acetic acid, be neutralized to pH value 6～7, discharging.Note is TMDEG-2.
Embodiment tri-:
First in reactor, pass into 67.8 grams of TMDD, add the sodium hydroxide of 0.2404 gram, with after N2 displacement, reactor heats up, and starts to pass into oxyethane when reactor is warming up to 80 ℃ in reactor, and add-on is 52.4 grams.Control reaction pressure and be less than 0.4Mpa, 100 ℃-110 ℃ of temperature of reaction are carried out polyreaction, after treating that oxyethane all adds, are incubated aging 30min.Agingly be cooled to 70 ℃ after complete, with Glacial acetic acid, be neutralized to pH value 6～7, discharging.Note is TMDEG-3.
Embodiment tetra-
By 147 grams, 240 grams of AL (molecular weight 2400), 0.1298 gram of TMDEG-1 and water, add reactor, turn on agitator, slowly heats up, and after polyethers dissolves completely, then is warming up to 90 ℃, the aqueous solution 48.2g that contains 5.35 grams of ammonium persulphates 90 ℃ of droppings; Time for adding is 3.5 hours.After ammonium persulfate solution drips 2min, start to drip 39.2 grams of the aqueous solution that contain 19.6 grams of MA, time for adding is 3 hours.Treat that ammonium persulfate solution keeps 1 hour in 90 ℃ after dripping.Be cooled to below 30 ℃, with 30% sodium hydroxide solution, being neutralized to pH value is 7, is polycarboxylate water-reducer product.
Embodiment five
By 147 grams, 240 grams of AL (molecular weight 2400), 0.1298 gram of TMDEG-2 and water, add reactor, turn on agitator, slowly heats up, and after polyethers dissolves completely, then is warming up to 90 ℃, the aqueous solution 48.2g that contains 5.35 grams of ammonium persulphates 90 ℃ of droppings; Time for adding is 3.5 hours.After ammonium persulfate solution drips 2min, start to drip 39.2 grams of the aqueous solution that contain 19.6 grams of MA, time for adding is 3 hours.Treat that ammonium persulfate solution keeps 1 hour in 90 ℃ after dripping.Be cooled to below 30 ℃, with 30% sodium hydroxide solution, being neutralized to pH value is 7, is polycarboxylate water-reducer product.
Embodiment six
By 147 grams, 240 grams of MAL (molecular weight 2400), 0.1298 gram of TMDEG-3 and water, add reactor, turn on agitator, slowly heats up, and after polyethers dissolves completely, then is warming up to 80 ℃, the aqueous solution 48.2g that contains 5.35 grams of ammonium persulphates 80 ℃ of droppings; Time for adding is 3.5 hours.After ammonium persulfate solution drips 2min, start to drip 43.2 grams of the aqueous solution that contain 21.6 grams of AA, time for adding is 3 hours.Treat that ammonium persulfate solution keeps 1 hour in 80 ℃ after dripping.Be cooled to below 30 ℃, with 30% sodium hydroxide solution, being neutralized to pH value is 7, is polycarboxylate water-reducer product.
Embodiment seven
By 147 grams, 240 grams of MBL (molecular weight 2400), 0.1298 gram of TMDEG-3 and water, add reactor, turn on agitator, slowly heats up, and after polyethers dissolves completely, then is warming up to 80 ℃, the aqueous solution 48.2g that contains 5.35 grams of ammonium persulphates 80 ℃ of droppings; Time for adding is 3.5 hours.After ammonium persulfate solution drips 2min, start to drip 43.2 grams of the aqueous solution that contain 21.6 grams of AA, time for adding is 3 hours.Treat that ammonium persulfate solution keeps 1 hour in 80 ℃ after dripping.Be cooled to below 30 ℃, with 30% sodium hydroxide solution, being neutralized to pH value is 7, is polycarboxylate water-reducer product.
Embodiment eight
By 110 grams, 165 grams of AL (molecular weight 3300), 0.0897 gram of TMDEG-2 and water, add reactor, turn on agitator, slowly heats up, and after polyethers dissolves completely, then is warming up to 80 ℃, the aqueous solution 35.5g that contains 3.58 grams of ammonium persulphates 80 ℃ of droppings; Time for adding is 3.5 hours.After ammonium persulfate solution drips 2min, start to drip 28.8 grams of the aqueous solution that contain 14.4 grams of AA, time for adding is 3 hours.Treat that ammonium persulfate solution keeps 1 hour in 80 ℃ after dripping.Be cooled to below 30 ℃, with 30% sodium hydroxide solution, being neutralized to pH value is 7, is polycarboxylate water-reducer product.
Embodiment nine
By 73.5 grams, 120 grams of BL (molecular weight 1200), 0.0649 gram of TMDEG-1 and water, add reactor, turn on agitator, slowly heats up, and after polyethers dissolves completely, then is warming up to 80 ℃, the aqueous solution 24.1g that contains 2.67 grams of ammonium persulphates 80 ℃ of droppings; Time for adding is 3.5 hours.After ammonium persulfate solution drips 2min, start to drip 43.2 grams of the aqueous solution that contain 21.6 grams of AA, time for adding is 3 hours.Treat that ammonium persulfate solution keeps 1 hour in 80 ℃ after dripping.Be cooled to below 30 ℃, with 30% sodium hydroxide solution, being neutralized to pH value is 7, is polycarboxylate water-reducer product.
By embodiment tetra-to nine prepared poly carboxylic acid series water reducers, be applied to P.O42.5 cement, measure the data such as its air content, concrete slump, divergence and the slump after 1 hour, divergence.(volume folding be admittedly cement 0.3%).
Table 1 concrete 's air-containing, the slump, divergence and 28d ultimate compression strength data
| Embodiment | Four | Five | Six | Seven | Eight | Nine |
| Water-reducing rate % | 32 | 32 | 36 | 40 | 37 | 35 |
| Air content % | 2.6 | 2.4 | 2.0 | 1.7 | 2.3 | 2.2 |
| Initial slump mm | 218 | 218 | 222 | 230 | 225 | 220 |
| Initial extension degree mm | 625 | 622 | 627 | 623 | 624 | 621 |
| 1 hour slump mm | 197 | 199 | 212 | 224 | 210 | 209 |
| 1 hour divergence mm | 559 | 586 | 602 | 613 | 610 | 592 |
| 28d compressive strength rate % | 153 | 155 | 162 | 160 | 157 | 162 |
As can be seen from the table, by present method, prepare 2,4,7,9-tetramethyl--5-decine-4,7-bis-polyoxyethylenated alcohol, and this polyethers is applied to polycarboxylate water-reducer prepared by present method, synthetic water reducer air content is low, minimum 1.7%, the highest by 2.6%, the slump keeps, and 28d compressive strength rate is large.
Claims (3)
1. a functionalised polyethers, is characterized in that: this polyethers is with oxyethane and 2,4,7,9-tetramethyl--5-decine-4, and 7-glycol is raw material, under following reaction conditions, reacts:
A) polyethers is by oxyethane and 2,4,7,9-tetramethyl--5-decine-4,7-glycol reacts under catalyst action, and temperature of reaction is 80-120 ℃, and reaction pressure is 0.1-0.4MPa, and 2,4,7,9-tetramethyl--5-decine-4, the mole ratio of 7-glycol and oxyethane is 1:1-4;
B) used catalyst is one or more mixing in sodium hydroxide, potassium hydroxide, sodium cyanide, and catalyst levels is the 0.005-0.2% of reactant total mass, and the synthetic polyethers of described method is TMDEG, has following structure:
Wherein, the real number that n is 1-4.
2. adopt polyethers as claimed in claim 1 to prepare a method for water reducer, it is characterized in that: this polyethers is applied in polycarboxylic acid series, under the condition being existed at initiator by each comonomer, copolyreaction in the solvent stirring and obtaining, is specially:
Described comonomer is to consist of component A and B component, and the quality of component A accounts for the 60-90% of monomer total mass, and all the other are B component, wherein,
Component A: be the mixture of component A1 and component A2, A1 is selected from the polyether monomer that molecular weight is 400-4000, is selected from one or more mixing in propylene alcohol ether, methacrylic alcohol ether, butylene alcohol ether, methyl butene alcohol ether; Component A2 is TMDEG;
B component: B component is selected from one or more mixing in methacrylic acid, vinylformic acid, toxilic acid, maleic anhydride, Hydroxyethyl acrylate, Propylene glycol monoacrylate, acrylamido-methyl propane sulfonic acid, methylpropene sodium sulfonate;
Described solvent is water; Described polymeric reaction temperature is 50-90 ℃, and the reaction times is 3-8 hour;
After polyreaction completes, in copolymerization product, add sodium hydroxide solution neutralization, regulate pH value at 6-7.
3. polyethers according to claim 2 is prepared the method for water reducer, it is characterized in that: the initiator that described copolyreaction adopts consists of Oxidizing and Reducing Agents, wherein oxygenant is selected from one or more mixing in Sodium Persulfate, ammonium persulphate, Potassium Persulphate or hydrogen peroxide; Reductive agent is selected from one or more mixing in xitix, sodium bisulfite, glucose, rongalite, and in reaction system, the total mass of redox agent is the 1-8% of monomer total mass.
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| CN104004180A (en) * | 2014-05-06 | 2014-08-27 | 盘锦富隆化工有限公司 | Polycarboxylate water-reducer macromonomer |
| CN105461917A (en) * | 2015-11-13 | 2016-04-06 | 鑫统领建材集团有限公司 | Compatibility improving agent and preparation method and application thereof |
| CN106116226A (en) * | 2016-06-26 | 2016-11-16 | 石家庄协耦化学科技有限公司 | Improve workability, encapsulated polycarboxylate water-reducer and preparation method thereof |
| CN109320683A (en) * | 2018-09-28 | 2019-02-12 | 福建华夏蓝新材料科技有限公司 | A kind of aqueous polyurethane dispersion of low surface tension and preparation method thereof |
| CN111378115A (en) * | 2018-12-29 | 2020-07-07 | 江苏苏博特新材料股份有限公司 | Glycosyl water reducing agent and preparation method thereof |
| CN112794688A (en) * | 2021-01-29 | 2021-05-14 | 武汉理工大学 | Early-strength low-shrinkage concrete for prefabricated parts and preparation process thereof |
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| CN109320683A (en) * | 2018-09-28 | 2019-02-12 | 福建华夏蓝新材料科技有限公司 | A kind of aqueous polyurethane dispersion of low surface tension and preparation method thereof |
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| CN111378115A (en) * | 2018-12-29 | 2020-07-07 | 江苏苏博特新材料股份有限公司 | Glycosyl water reducing agent and preparation method thereof |
| CN112794688A (en) * | 2021-01-29 | 2021-05-14 | 武汉理工大学 | Early-strength low-shrinkage concrete for prefabricated parts and preparation process thereof |
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