CN103601881B - A kind of functionalised polyethers and the preparation method be applied in water reducer thereof - Google Patents
A kind of functionalised polyethers and the preparation method be applied in water reducer thereof Download PDFInfo
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Abstract
The invention discloses a kind of preparation method of functionalised polyethers, and apply the preparation method of poly carboxylic acid series water reducer of this polyethers.The preparation of polyethers is that raw material addition of ethylene oxide obtains with 2,4,7,9-tetramethyl--5-decine-4,7-glycol, and production technique is simple, harmless to humans and animals, environmental sound, and environmental protection, has the function of froth breaking; The preparation of water reducer is aggregated on water reducer molecular structure by this functionalised polyethers, the water reducer of synthesis itself is made namely to possess the function of froth breaking, reduce the air content in concrete, the water reducer air content of synthesis is minimum is 1.7%, impart the better serviceability of concrete, be conducive to the water-reducing effect of water reducer simultaneously and keep effect.
Description
Technical field: the present invention relates to a kind of concrete admixture, is specifically related to the preparation method of the polyethers of synthesizing polycarboxylic acid dehydragent and uses this polyethers to prepare the method for poly carboxylic acid series water reducer.
Background technology: when polycarboxylate water-reducer is used for concrete batching, has that low-dosage, dissemination are strong, little loss of slump, early strength strengthen and the characteristic such as good endurance.In addition, be also improved concrete hole structure and compaction rate, control the function of the problems such as concrete bleed, slow setting, bleeding better, become indispensable BSA in concrete mix.But many polycarboxylate dehydragent surfactivitys are high, guarantor's bubble property is good, and when being directly used in concrete, concrete 's air-containing is large, intensity is low, and therefore required Compounded Antifoamer uses, and to reduce concrete 's air-containing, improve concrete strength.The polycarboxylate water-reducer that defoamer is composite, air pocket unnecessary in the concrete that both disappeared, simultaneously owing to decreasing the air content in polycarboxylate water-reducer, improves concrete hole structure and compaction rate, improves 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 gradual loss also increases thereupon.Therefore, develop and the air content in concrete can be adjusted to suitable amount, and the polycarboxylate water-reducer of Concrete Structure intensity has become the emphasis of research.
Not by composite, solving the large problem of polycarboxylate concrete air content by the method for synthesis, is generally 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 introduced can not have negative impact to concrete serviceability, can not have impact to the solvability of polycarboxylate water-reducer.2,4,7,9-tetramethyl--5-decine-4, it is wetting that 7-glycol is that one has, froth breaking, improves dispersed, effectively can 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, after oxyethane a small amount of in addition, improve that it is water-soluble, the polyethers of synthesis itself also still has their defoaming function, directly apply to polymerization system, the water reducer of synthesis itself is also had and controls bubble function, further increase the performance of poly carboxylic acid series water reducer.
Summary of the invention:
Goal of the invention: the preparation method that the object of this invention is to provide a kind of functional polyethers and the method for 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 water reducer that most importantly air content is suitable.
Technical scheme: the present invention implements by the following technical programs:
A kind of functionalised polyethers, is characterized in that: this polyethers, reacts for raw material at the following reaction conditions with oxyethane and 2,4,7,9-tetramethyl--5-decine-4,7-glycol:
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 DEG C, and reaction pressure is 0.1-0.4MPa, and 2, the mole ratio of 4,7,9-tetramethyl--5-decine-4,7-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 polyethers of described method synthesis is TMDEG, has following structure:
Wherein, n is the real number of 1-4.
This polyethers is applied in poly carboxylic acid series water reducer, and by each comonomer under initiator existent condition, copolyreaction and obtaining in the solvent stirred, is specially:
Described comonomer is made up 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 propanesulfonic acid, methylpropene sodium sulfonate;
Described solvent is water; Described polymeric reaction temperature is 50-90 DEG C, and the reaction times is 3-8 hour;
After polyreaction completes, in copolymerization product, add sodium hydroxide solution neutralization, adjust ph is at 6-7.
The initiator that described copolyreaction adopts is made up 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; The polyethers of synthesis 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 lower than 3%, can be suitable for high-strength, super high strength concrete.Impart the better serviceability of concrete;
3, this froth breaking polyethers participates in polymerization, changes polycarboxylate water-reducer molecular structure, changes the density of side chain on unit length chain link, be conducive to water reducer molecule slow releasing in concrete, is conducive to the water-reducing effect of water reducer and keeps effect.
4, water reducer of the present invention directly introduces froth breaking polyethers in the molecule, adds 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 that can be polymerized directly can introduce TMDEG;
6, namely water reducer of the present invention introduces defoamer in polymerization, then need not add defoamer again, so cost does not increase when later stage and other compounding concrete admixtures use;
7, be directly quote defoamer in polymerization, improve the viscosity of concrete mortar, improve concrete workability;
8, improve the dispersiveness between traditional defoamer and admixture, reach the shelf-time to the effect of result without impact.
Embodiment: the invention will be further described below in conjunction with example:
The present invention relates to two steps, one is the preparation of this kind of functionalised polyethers, and two is preparations of the poly carboxylic acid series water reducer comprising this polyether monomer.The preparation of described polyethers be with oxyethane and 2,4,7,9-tetramethyl--5-decine-4,7-glycol for raw material, react at the following reaction conditions:
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 DEG C, and reaction pressure is 0.1-0.4MPa, and 2, the mole ratio of 4,7,9-tetramethyl--5-decine-4,7-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 DEG C; Reaction pressure is preferably 0.3-0.4MPa; Catalyst levels is preferably 0.15-0.2%.The polyethers of synthesis has following structure:
Wherein, n is the real number of 1-4.
TMDEG prepared by the present invention is a kind of solvability defoamer, just can reduce the air content of poly carboxylic acid series water reducer, improve workability when polymerization volume is extremely low.The preparation of water reducer by each copolymerization monomer, is stirred and carries out copolyreaction in a solvent and obtain under initiator existent condition:
Described comonomer is made up 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 propanesulfonic acid, methylpropene sodium sulfonate;
Described solvent is water; Described polymeric reaction temperature is 50-90 DEG C, and the time is 3-8 hour;
After polyreaction completes, in copolymerization product, add sodium hydroxide solution neutralization, adjust ph is at 6-7.Preferred technical scheme, the initiation method that described copolyreaction adopts is redox system, and initiator is made up of Oxidizing and Reducing Agents, and wherein oxygenant is selected from the one 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, can select to add and do not add according to the kind of oxygenant, 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 add together with solvent in reactor, is warming up to component A and all dissolves.Preferred technical scheme, described component A1 concentration is in a solvent 60-70%, component A2 concentration is in a solvent 0.1%.
In technique scheme, the feed way of B component and initiator, for being added drop-wise in reactor, first dripping 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, represent " propylene alcohol ether " with AL below; Represent " methacrylic alcohol ether " with MAL; Represent " butylene alcohol ether " with BL; Represent " methyl butene alcohol ether " with MBL; Represent " ethoxylation 2,4,7,9-tetramethyl--5-decine-4,7-glycol " with TMDD, represent " ethoxylation 2,4,7,9-tetramethyl--5-decine-4,7-glycol ethers " with TMDEG; Represent " maleic anhydride " with MA; Represent " vinylformic acid " with AA; Represent " ammonium persulphate " with APS.
Embodiment one:
First in reactor, pass into 67.8 grams of TMDD, add the sodium hydroxide of 0.162 gram, use N
2after displacement, reactor heats up, and start when reactor is warming up to 80 DEG C to pass into oxyethane in reactor, add-on is 13.2 grams.Control reaction pressure and be less than 0.4MPa, temperature of reaction 100 DEG C-110 DEG C carries out polyreaction, after treating that oxyethane all adds, is incubated aging 30min.Aging complete after be cooled to 70 DEG C, be neutralized to pH value 6 ~ 7 with Glacial acetic acid, discharging.Be denoted as TMDEG-1.
Embodiment two:
First in reactor, pass into 67.8 grams of TMDD, add the sodium hydroxide of 0.2201 gram, use N
2after displacement, reactor heats up, and start when reactor is warming up to 80 DEG C to pass into oxyethane in reactor, add-on is 42.24 grams.Control reaction pressure and be less than 0.4Mpa, temperature of reaction 100 DEG C-110 DEG C carries out polyreaction, after treating that oxyethane all adds, is incubated aging 30min.Aging complete after be cooled to 70 DEG C, be neutralized to pH value 6 ~ 7 with Glacial acetic acid, discharging.Be denoted as TMDEG-2.
Embodiment three:
First in reactor, pass into 67.8 grams of TMDD, add the sodium hydroxide of 0.2404 gram, use N
2after displacement, reactor heats up, and start when reactor is warming up to 80 DEG C to pass into oxyethane in reactor, add-on is 52.4 grams.Control reaction pressure and be less than 0.4Mpa, temperature of reaction 100 DEG C-110 DEG C carries out polyreaction, after treating that oxyethane all adds, is incubated aging 30min.Aging complete after be cooled to 70 DEG C, be neutralized to pH value 6 ~ 7 with Glacial acetic acid, discharging.Be denoted as TMDEG-3.
Embodiment four
By 240 grams of AL (molecular weight 2400), 0.1298 gram of TMDEG-1 and 147 grams, water, add reactor, turn on agitator, slow intensification, after polyethers dissolves completely, then be warming up to 90 DEG C, drip the aqueous solution 48.2g containing 5.35 grams of ammonium persulphates at 90 DEG C; Time for adding is 3.5 hours.Drip after 2min until ammonium persulfate solution, start to drip the aqueous solution 39.2 grams containing 19.6 grams of MA, time for adding is 3 hours.Treat that ammonium persulfate solution keeps 1 hour in 90 DEG C after dripping.Be cooled to less than 30 DEG C, being neutralized to pH value with 30% sodium hydroxide solution is 7, is polycarboxylate water-reducer product.
Embodiment five
By 240 grams of AL (molecular weight 2400), 0.1298 gram of TMDEG-2 and 147 grams, water, add reactor, turn on agitator, slow intensification, after polyethers dissolves completely, then be warming up to 90 DEG C, drip the aqueous solution 48.2g containing 5.35 grams of ammonium persulphates at 90 DEG C; Time for adding is 3.5 hours.Drip after 2min until ammonium persulfate solution, start to drip the aqueous solution 39.2 grams containing 19.6 grams of MA, time for adding is 3 hours.Treat that ammonium persulfate solution keeps 1 hour in 90 DEG C after dripping.Be cooled to less than 30 DEG C, being neutralized to pH value with 30% sodium hydroxide solution is 7, is polycarboxylate water-reducer product.
Embodiment six
By 240 grams of MAL (molecular weight 2400), 0.1298 gram of TMDEG-3 and 147 grams, water, add reactor, turn on agitator, slow intensification, after polyethers dissolves completely, then be warming up to 80 DEG C, drip the aqueous solution 48.2g containing 5.35 grams of ammonium persulphates at 80 DEG C; Time for adding is 3.5 hours.Drip after 2min until ammonium persulfate solution, start to drip the aqueous solution 43.2 grams containing 21.6 grams of AA, time for adding is 3 hours.Treat that ammonium persulfate solution keeps 1 hour in 80 DEG C after dripping.Be cooled to less than 30 DEG C, being neutralized to pH value with 30% sodium hydroxide solution is 7, is polycarboxylate water-reducer product.
Embodiment seven
By 240 grams of MBL (molecular weight 2400), 0.1298 gram of TMDEG-3 and 147 grams, water, add reactor, turn on agitator, slow intensification, after polyethers dissolves completely, then be warming up to 80 DEG C, drip the aqueous solution 48.2g containing 5.35 grams of ammonium persulphates at 80 DEG C; Time for adding is 3.5 hours.Drip after 2min until ammonium persulfate solution, start to drip the aqueous solution 43.2 grams containing 21.6 grams of AA, time for adding is 3 hours.Treat that ammonium persulfate solution keeps 1 hour in 80 DEG C after dripping.Be cooled to less than 30 DEG C, being neutralized to pH value with 30% sodium hydroxide solution is 7, is polycarboxylate water-reducer product.
Embodiment eight
By 165 grams of AL (molecular weight 3300), 0.0897 gram of TMDEG-2 and 110 grams, water, add reactor, turn on agitator, slow intensification, after polyethers dissolves completely, then be warming up to 80 DEG C, drip the aqueous solution 35.5g containing 3.58 grams of ammonium persulphates at 80 DEG C; Time for adding is 3.5 hours.Drip after 2min until ammonium persulfate solution, start to drip the aqueous solution 28.8 grams containing 14.4 grams of AA, time for adding is 3 hours.Treat that ammonium persulfate solution keeps 1 hour in 80 DEG C after dripping.Be cooled to less than 30 DEG C, being neutralized to pH value with 30% sodium hydroxide solution is 7, is polycarboxylate water-reducer product.
Embodiment nine
By 120 grams of BL (molecular weight 1200), 0.0649 gram of TMDEG-1 and 73.5 grams, water, add reactor, turn on agitator, slow intensification, after polyethers dissolves completely, then be warming up to 80 DEG C, drip the aqueous solution 24.1g containing 2.67 grams of ammonium persulphates at 80 DEG C; Time for adding is 3.5 hours.Drip after 2min until ammonium persulfate solution, start to drip the aqueous solution 43.2 grams containing 21.6 grams of AA, time for adding is 3 hours.Treat that ammonium persulfate solution keeps 1 hour in 80 DEG C after dripping.Be cooled to less than 30 DEG C, being neutralized to pH value with 30% sodium hydroxide solution is 7, is polycarboxylate water-reducer product.
Poly carboxylic acid series water reducer obtained by embodiment four to nine is applied to P.O42.5 cement, measures the data such as its air content, concrete slump, divergence and the slump after 1 hour, divergence.(volume folding is 0.3% of cement admittedly).
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, prepared by present method 2,4,7,9-tetramethyl--5-decine-4,7-bis-polyoxyethylenated alcohol, and the polycarboxylate water-reducer this polyethers being applied to prepared by present method, the water reducer air content of synthesis is low, minimum 1.7%, the highest by 2.6%, slump retention is good, and 28d compressive strength rate is large.
Claims (2)
1. functionalised polyethers prepares a method for water reducer, it is characterized in that: this polyethers, reacts for raw material at the following reaction conditions with oxyethane and 2,4,7,9-tetramethyl--5-decine-4,7-glycol:
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 DEG C, and reaction pressure is 0.1-0.4MPa, and 2, the mole ratio of 4,7,9-tetramethyl--5-decine-4,7-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 polyethers of described method synthesis is TMDEG, has following structure:
Wherein, n is the real number of 1-4;
This polyethers is applied in poly carboxylic acid series water reducer, and by each comonomer under initiator existent condition, copolyreaction and obtaining in the solvent stirred, is specially:
Described comonomer is made up 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 propanesulfonic acid, methylpropene sodium sulfonate;
Described solvent is water; Described polymeric reaction temperature is 50-90 DEG C, and the reaction times is 3-8 hour;
After polyreaction completes, in copolymerization product, add sodium hydroxide solution neutralization, adjust ph is at 6-7.
2. functionalised polyethers according to claim 1 prepares the method for water reducer, it is characterized in that: the initiator that described copolyreaction adopts is made up 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 |
| CN105461917B (en) * | 2015-11-13 | 2018-02-16 | 青神鑫统领建材有限公司 | Compatibility improvement agent and its production and use |
| CN106116226B (en) * | 2016-06-26 | 2018-10-16 | 石家庄协耦化学科技有限公司 | Improve workability, encapsulated polycarboxylate water-reducer and preparation method thereof |
| CN109320683B (en) * | 2018-09-28 | 2021-03-19 | 福建华夏蓝新材料科技有限公司 | Low-surface-tension aqueous polyurethane dispersion and preparation method thereof |
| CN111378115B (en) * | 2018-12-29 | 2023-01-03 | 江苏苏博特新材料股份有限公司 | Glycosyl water reducing agent and preparation method thereof |
| CN112794688B (en) * | 2021-01-29 | 2021-11-16 | 武汉理工大学 | Early-strength low-shrinkage concrete for prefabricated parts and preparation process thereof |
| CN117776418A (en) * | 2023-12-29 | 2024-03-29 | 陕西金标实业有限公司 | Neutral Gao Wenyi salt scale inhibitor and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3268593A (en) * | 1961-06-26 | 1966-08-23 | Cumberland Chemical Corp | Ethylene oxide adducts of tertiary acetylenic alcohols |
| US4209336A (en) * | 1977-12-12 | 1980-06-24 | W. R. Grace & Co. | Method of enhancing the compressive strength of hydraulic cement composition |
| US6313182B1 (en) * | 1999-05-04 | 2001-11-06 | Air Products And Chemicals, Inc. | Acetylenic diol ethylene oxide/propylene oxide adducts and processes for their manufacture |
| CN102140019A (en) * | 2010-11-24 | 2011-08-03 | 辽宁奥克化学股份有限公司 | Polycarboxylic acid water reducing agent and preparation method thereof |
-
2013
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3268593A (en) * | 1961-06-26 | 1966-08-23 | Cumberland Chemical Corp | Ethylene oxide adducts of tertiary acetylenic alcohols |
| US4209336A (en) * | 1977-12-12 | 1980-06-24 | W. R. Grace & Co. | Method of enhancing the compressive strength of hydraulic cement composition |
| US6313182B1 (en) * | 1999-05-04 | 2001-11-06 | Air Products And Chemicals, Inc. | Acetylenic diol ethylene oxide/propylene oxide adducts and processes for their manufacture |
| CN102140019A (en) * | 2010-11-24 | 2011-08-03 | 辽宁奥克化学股份有限公司 | Polycarboxylic acid water reducing agent and preparation method thereof |
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