CN102604005A - Preparation method of strengthening and toughening polycarboxylate water reducing agent - Google Patents
Preparation method of strengthening and toughening polycarboxylate water reducing agent Download PDFInfo
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Abstract
The invention relates to a preparation method of a strengthening and toughening polycarboxylate water reducing agent. The method comprises the following steps of: oxidizing graphite powder by using concentrated sulfuric acid and potassium permanganate, then carrying out ultrasonic separation to obtain graphene oxide structurally containing carboxyl, hydroxyl, epoxy group and the like, and then, subjecting graphene oxide and allyl polyoxylethylene ether to esterification reaction under the action of ultrasonic; then carrying out free radical copolymerization reaction with methacrylic acid and sodium methylacrylsulfonate under the initiation of ammonium persulfate to obtain the strengthening and toughening polycarboxylate water reducing agent. The method provided by the invention has the innovation points as follows: a graphene oxide structure is introduced to the molecule of the polycarboxylate water reducing agent through oxidation, separation, esterification and free radical copolymerization reaction, so that the strength of concrete is increased by the high water-reducing rate of the water reducing agent, and in addition, the graphene also has strengthening and toughening effects for the concrete.
Description
Technical field
The invention belongs to the technical field of concrete additives in the fine chemistry industry, be specifically related to a kind of preparation method that can increase concrete strength and flexible poly carboxylic acid series water reducer.
Background technology
Concrete still is the topmost material of construction in the world today, and concrete production needs a large amount of cement, sandstone etc., and the resource and the energy that these preparing raw material process need consumption are a large amount of also can produce huge environmental pollution simultaneously.In the today that reduces resource consumption, cuts down the consumption of energy and advocate low-carbon economy, improve concrete intensity and time limit of service, the consumption that reduces build concrete is to realize one of major measure that low-carbon economy, minimizing are polluted.Use is efficient, the reinforcing type polycarboxylic acid series water reducer is the main method that improves mechanical performance of concrete, reduces consumptions such as concrete and cement, and therefore, the additive that research and development can improve concrete strength has received attention both domestic and external.The main method that improves concrete strength at present is to add to have the admixture that increases concrete strength, and this also is the focus of domestic and international research.
Graphite is a kind of material that obtains easily; It is by pushing away folded forming with the plane carbon atom of cellular ordered arrangement from level to level; Reactive force between layer and the layer mainly is weak Van der Waals force, peels off thinner graphite flake layer than being easier to, and is exactly Graphene if graphite is stripped from into individual layer.Through functional modification to Graphene, can prepare the graphene nano material behind the modification, have huge application potential at aspects such as strengthening polymer composite, conducting polymer composite, catalytic material.Graphene oxide is a kind of hydroaropic substance with groups such as great amount of hydroxy group and carboxyls; Closely arrange the individual layer bi-dimensional cellular shape crystalline network of formation for carbon atom; Have huge specific surface area and excellent mechanical property; Therefore the wide material sources and the environmentally safe of graphite, will have very big prospect in the use graphene oxide modified polycarboxylic acid based water reducer simultaneously.
Summary of the invention
The object of the present invention is to provide and a kind ofly can significantly put forward concrete intensity and toughness, improve the preparation method of the enhancing toughening type poly carboxylic acid series water reducer of mechanical properties of concrete and weather resistance.
For achieving the above object, the technical scheme that the present invention adopts is:
1) by mass fraction 6 parts of Graphite Powder 99s and 3 parts of SODIUMNITRATE under agitation being joined temperature is in 60 parts of vitriol oils of 5 ℃, mixes the back and slowly adds 18 parts of potassium permanganate, at room temperature reacts 10 hours; 200 parts of deionized waters of adding slowly are warming up to 68 ℃ and continue reaction 4 hours, drip the superoxol of 20 parts of massfractions 30% then; After the ultrasonic dispersing 30 minutes; Centrifuging, repetitive scrubbing is removed sulfuric acid, at 60 ℃ of dry down graphene oxides that get;
2) get 20～30 parts of allyl polyethenoxy ethers by mass fraction; 0.5 mixing and stir ,～2.0 parts of graphene oxides and 0.2～1.0 part of vitriol oil be warming up to 60～75 ℃; Insulation and ultrasonication 1～1.5 hour obtain graphene oxide modification allyl polyethenoxy ether;
3) in graphene oxide modification allyl polyethenoxy ether, add 1.72～5.16 parts of methylacrylic acids by mass fraction again, 0.16～0.95 part of methylpropene sodium sulfonate, 0.02～0.08 part of Resorcinol and 40～70 parts of deionized waters also continue ultrasonication and obtained mixed monomer solution in 0.5～1.0 hour;
4) 30～40 parts of deionized waters are added in the reaction kettle; Drip mixed monomer solution and initiator solution that step 3) is processed when being warming up to 80～90 ℃ respectively, the dropping time of mixed monomer solution is 1.0～1.5 hours, and the dropping time of initiator solution is 1.5～2.0 hours; Insulation reaction is 2.5～3 hours behind reinforced the finishing; Be cooled to 45 ℃, regulate pH=7.0, promptly get and strengthen the toughening type poly carboxylic acid series water reducer with sodium hydroxide solution.
The granularity of described Graphite Powder 99＜30 micron.
Described vitriol oil massfraction is 98%.
Described initiator solution is by mass fraction 0.2～0.4 part of ammonium persulphate to be dissolved in 20～30 parts of deionized waters to process.
The massfraction of described sodium hydroxide solution is 25%.
The present invention carries out carrying out UW after the oxidation with the vitriol oil and potassium permanganate to Graphite Powder 99 to separate; Obtained containing on the structure graphene oxide of carboxyl, hydroxyl, epoxy group(ing) etc., under action of ultrasonic waves, made graphene oxide and allyl polyethenoxy ether carry out esterification again.Under action of evocating, carry out free radical copolymerization then, obtain having the poly carboxylic acid series water reducer that strengthens toughening effect with methylacrylic acid and methylpropene sodium sulfonate.Be incorporated into the graphene oxide structure in the poly carboxylic acid series water reducer molecule through oxidation, separation, esterification and free radicals copolymerization reaction; Except that the high water reducing rate of crossing the gained water reducer caused the concrete strength raising, Graphene itself also had the toughness reinforcing effect of enhancing to concrete.Water reducer of the present invention has following characteristics: (1) volume is low, and water-reducing rate is high, and when the solid volume of folding was gelatinous material 0.17%, water-reducing rate reached 33%.(2) the initial clean slurry degree of mobilization of cement can reach (W/C=0.29) more than 300 millimeters, reduces 7.5% in 2 hours, and concrete function of slump protection is good, and the mix concrete slump reduced 9% at 4 hours.(3) compare with the similar poly carboxylic acid series water reducer of not introducing Graphene, concrete 3 days (3d), 7 days (7d) and 28 days (28d) folding strengths improve 4.8%, 6.6% and 9.6% respectively, and ultimate compression strength improves 4.5%, 6.2% and 11.3% respectively.
Description of drawings
Fig. 1 is a synthetic route chart of the present invention.
Embodiment
Below in conjunction with accompanying drawing the present invention is done further explain.
Embodiment 1: referring to Fig. 1,
1) by mass fraction the Graphite Powder 99 of 6 parts of granularity＜30 micron and 3 parts of SODIUMNITRATE under agitation being joined temperature is that 5 ℃, massfraction are in 60 parts of vitriol oils of 98%; Mix the back and slowly add 18 parts of potassium permanganate, at room temperature reacted 200 parts of deionized waters of adding slowly 10 hours; Be warming up to 68 ℃ and continue reaction 4 hours; Drip the superoxol of 20 parts of massfractions 30% then, ultrasonic dispersing is after 30 minutes, centrifuging; Repetitive scrubbing is removed sulfuric acid, at 60 ℃ of dry down graphene oxides that get;
2) get 20 parts of allyl polyethenoxy ethers by mass fraction, 0.5 part of graphene oxide and 0.2 part of massfraction are that 98% the vitriol oil mixes and stirs and is warming up to 60 ℃, and insulation and ultrasonication 1 hour obtain graphene oxide modification allyl polyethenoxy ether;
3) press mass fraction again and in graphene oxide modification allyl polyethenoxy ether, add 1.72 parts of methylacrylic acids, 0.16 part of methylpropene sodium sulfonate, 0.02 part of Resorcinol and 40 parts of deionized waters also continue ultrasonication and obtained mixed monomer solution in 0.5 hour;
4) 30 parts of deionized waters are added in the reaction kettle; Drip mixed monomer solution and initiator solution that step 3) is processed when being warming up to 80 ℃ respectively, the dropping time of mixed monomer solution is 1 hour, and the dropping time of initiator solution is 1.6 hours; Insulation reaction is 2.5 hours behind reinforced the finishing; Be cooled to 45 ℃, the use massfraction is 25% sodium hydroxide solution adjusting pH=7.0, promptly gets to strengthen the toughening type poly carboxylic acid series water reducer.
Wherein, initiator solution is by mass fraction 0.2 part of ammonium persulphate to be dissolved in 20 parts of deionized waters to process.
Embodiment 2:
1) by mass fraction the Graphite Powder 99 of 6 parts of granularity＜30 micron and 3 parts of SODIUMNITRATE under agitation being joined temperature is that 5 ℃, massfraction are in 60 parts of vitriol oils of 98%; Mix the back and slowly add 18 parts of potassium permanganate, at room temperature reacted 200 parts of deionized waters of adding slowly 10 hours; Be warming up to 68 ℃ and continue reaction 4 hours; Drip the superoxol of 20 parts of massfractions 30% then, ultrasonic dispersing is after 30 minutes, centrifuging; Repetitive scrubbing is removed sulfuric acid, at 60 ℃ of dry down graphene oxides that get;
2) get 24 parts of allyl polyethenoxy ethers by mass fraction; 0.8 part graphene oxide and 0.4 part of massfraction are 98% the vitriol oil to be mixed and stirs and be warming up to 63 ℃; Insulation and ultrasonication 1.2 hours obtain graphene oxide modification allyl polyethenoxy ether;
3) press mass fraction again and in graphene oxide modification allyl polyethenoxy ether, add 2.58 parts of methylacrylic acids, 0.16 part of methylpropene sodium sulfonate, 0.04 part of Resorcinol and 45 parts of deionized waters also continue ultrasonication and obtained mixed monomer solution in 0.7 hour;
4) 32 parts of deionized waters are added in the reaction kettle; Drip mixed monomer solution and initiator solution that step 3) is processed when being warming up to 82 ℃ respectively, the dropping time of mixed monomer solution is 1.3 hours, and the dropping time of initiator solution is 1.5 hours; Insulation reaction is 3 hours behind reinforced the finishing; Be cooled to 45 ℃, the use massfraction is 25% sodium hydroxide solution adjusting pH=7.0, promptly gets to strengthen the toughening type poly carboxylic acid series water reducer.
Wherein, initiator solution is by mass fraction 0.24 part of ammonium persulphate to be dissolved in 22 parts of deionized waters to process.
Embodiment 3:
1) by mass fraction the Graphite Powder 99 of 6 parts of granularity＜30 micron and 3 parts of SODIUMNITRATE under agitation being joined temperature is that 5 ℃, massfraction are in 60 parts of vitriol oils of 98%; Mix the back and slowly add 18 parts of potassium permanganate, at room temperature reacted 200 parts of deionized waters of adding slowly 10 hours; Be warming up to 68 ℃ and continue reaction 4 hours; Drip the superoxol of 20 parts of massfractions 30% then, ultrasonic dispersing is after 30 minutes, centrifuging; Repetitive scrubbing is removed sulfuric acid, at 60 ℃ of dry down graphene oxides that get;
2) get 28 parts of allyl polyethenoxy ethers by mass fraction; 1.2 part graphene oxide and 0.8 part of massfraction are 98% the vitriol oil to be mixed and stirs and be warming up to 68 ℃; Insulation and ultrasonication 1.3 hours obtain graphene oxide modification allyl polyethenoxy ether;
3) press mass fraction again and in graphene oxide modification allyl polyethenoxy ether, add 3.44 parts of methylacrylic acids, 0.47 part of methylpropene sodium sulfonate, 0.06 part of Resorcinol and 50 parts of deionized waters also continue ultrasonication and obtained mixed monomer solution in 0.9 hour;
4) 34 parts of deionized waters are added in the reaction kettle; Drip mixed monomer solution and initiator solution that step 3) is processed when being warming up to 84 ℃ respectively, the dropping time of mixed monomer solution is 1.3 hours, and the dropping time of initiator solution is 1.5 hours; Insulation reaction is 2.6 hours behind reinforced the finishing; Be cooled to 45 ℃, the use massfraction is 25% sodium hydroxide solution adjusting pH=7.0, promptly gets to strengthen the toughening type poly carboxylic acid series water reducer.
Wherein, initiator solution is by mass fraction 0.28 part of ammonium persulphate to be dissolved in 24 parts of deionized waters to process.
Embodiment 4:
1) by mass fraction the Graphite Powder 99 of 6 parts of granularity＜30 micron and 3 parts of SODIUMNITRATE under agitation being joined temperature is that 5 ℃, massfraction are in 60 parts of vitriol oils of 98%; Mix the back and slowly add 18 parts of potassium permanganate, at room temperature reacted 200 parts of deionized waters of adding slowly 10 hours; Be warming up to 68 ℃ and continue reaction 4 hours; Drip the superoxol of 20 parts of massfractions 30% then, ultrasonic dispersing is after 30 minutes, centrifuging; Repetitive scrubbing is removed sulfuric acid, at 60 ℃ of dry down graphene oxides that get;
2) get 30 parts of allyl polyethenoxy ethers by mass fraction; 2.0 part graphene oxide and 1.0 parts of massfractions are 98% the vitriol oil to be mixed and stirs and be warming up to 70 ℃; Insulation and ultrasonication 1.4 hours obtain graphene oxide modification allyl polyethenoxy ether;
3) press mass fraction again and in graphene oxide modification allyl polyethenoxy ether, add 5.16 parts of methylacrylic acids, 0.95 part of methylpropene sodium sulfonate, 0.08 part of Resorcinol and 55 parts of deionized waters also continue ultrasonication and obtained mixed monomer solution in 1.0 hours;
4) 36 parts of deionized waters are added in the reaction kettle; Drip mixed monomer solution and initiator solution that step 3) is processed when being warming up to 86 ℃ respectively, the dropping time of mixed monomer solution is 1.5 hours, and the dropping time of initiator solution is 2.0 hours; Insulation reaction is 2.7 hours behind reinforced the finishing; Be cooled to 45 ℃, the use massfraction is 25% sodium hydroxide solution adjusting pH=7.0, promptly gets to strengthen the toughening type poly carboxylic acid series water reducer.
Wherein, initiator solution is by mass fraction 0.32 part of ammonium persulphate to be dissolved in 28 parts of deionized waters to process.
Embodiment 5:
1) by mass fraction the Graphite Powder 99 of 6 parts of granularity＜30 micron and 3 parts of SODIUMNITRATE under agitation being joined temperature is that 5 ℃, massfraction are in 60 parts of vitriol oils of 98%; Mix the back and slowly add 18 parts of potassium permanganate, at room temperature reacted 200 parts of deionized waters of adding slowly 10 hours; Be warming up to 68 ℃ and continue reaction 4 hours; Drip the superoxol of 20 parts of massfractions 30% then, ultrasonic dispersing is after 30 minutes, centrifuging; Repetitive scrubbing is removed sulfuric acid, at 60 ℃ of dry down graphene oxides that get;
2) get 26 parts of allyl polyethenoxy ethers by mass fraction; 1.6 part graphene oxide and 0.8 part of massfraction are 98% the vitriol oil to be mixed and stirs and be warming up to 72 ℃; Insulation and ultrasonication 1.5 hours obtain graphene oxide modification allyl polyethenoxy ether;
3) press mass fraction again and in graphene oxide modification allyl polyethenoxy ether, add 3.44 parts of methylacrylic acids, 0.79 part of methylpropene sodium sulfonate, 0.06 part of Resorcinol and 60 parts of deionized waters also continue ultrasonication and obtained mixed monomer solution in 0.8 hour;
4) 38 parts of deionized waters are added in the reaction kettle; Drip mixed monomer solution and initiator solution that step 3) is processed when being warming up to 88 ℃ respectively, the dropping time of mixed monomer solution is 2.0 hours, and the dropping time of initiator solution is 1.5 hours; Insulation reaction is 2.8 hours behind reinforced the finishing; Be cooled to 45 ℃, the use massfraction is 25% sodium hydroxide solution adjusting pH=7.0, promptly gets to strengthen the toughening type poly carboxylic acid series water reducer.
Wherein, initiator solution is by mass fraction 0.36 part of ammonium persulphate to be dissolved in 26 parts of deionized waters to process.
Embodiment 6:
1) by mass fraction the Graphite Powder 99 of 6 parts of granularity＜30 micron and 3 parts of SODIUMNITRATE under agitation being joined temperature is that 5 ℃, massfraction are in 60 parts of vitriol oils of 98%; Mix the back and slowly add 18 parts of potassium permanganate, at room temperature reacted 200 parts of deionized waters of adding slowly 10 hours; Be warming up to 68 ℃ and continue reaction 4 hours; Drip the superoxol of 20 parts of massfractions 30% then, ultrasonic dispersing is after 30 minutes, centrifuging; Repetitive scrubbing is removed sulfuric acid, at 60 ℃ of dry down graphene oxides that get;
2) get 24 parts of allyl polyethenoxy ethers by mass fraction; 1.8 part graphene oxide and 0.6 part of massfraction are 98% the vitriol oil to be mixed and stirs and be warming up to 75 ℃; Insulation and ultrasonication 1.1 hours obtain graphene oxide modification allyl polyethenoxy ether;
3) press mass fraction again and in graphene oxide modification allyl polyethenoxy ether, add 4.3 parts of methylacrylic acids, 0.63 part of methylpropene sodium sulfonate, 6 parts of Resorcinol and 70 parts of deionized waters also continue ultrasonication and obtained mixed monomer solution in 1.0 hours;
4) 40 parts of deionized waters are added in the reaction kettle; Drip mixed monomer solution and initiator solution that step 3) is processed when being warming up to 90 ℃ respectively, the dropping time of mixed monomer solution is 1.4 hours, and the dropping time of initiator solution is 1.8 hours; Insulation reaction is 3 hours behind reinforced the finishing; Be cooled to 45 ℃, the use massfraction is 25% sodium hydroxide solution adjusting pH=7.0, promptly gets to strengthen the toughening type poly carboxylic acid series water reducer.
Wherein, initiator solution is by mass fraction 0.4 part of ammonium persulphate to be dissolved in 30 parts of deionized waters to process.
Claims (5)
1. preparation method who strengthens the toughening type poly carboxylic acid series water reducer is characterized in that:
1) by mass fraction 6 parts of Graphite Powder 99s and 3 parts of SODIUMNITRATE under agitation being joined temperature is in 60 parts of vitriol oils of 5 ℃, mixes the back and slowly adds 18 parts of potassium permanganate, at room temperature reacts 10 hours; 200 parts of deionized waters of adding slowly are warming up to 68 ℃ and continue reaction 4 hours, drip the superoxol of 20 parts of massfractions 30% then; After the ultrasonic dispersing 30 minutes; Centrifuging, repetitive scrubbing is removed sulfuric acid, at 60 ℃ of dry down graphene oxides that get;
2) get 20～30 parts of allyl polyethenoxy ethers by mass fraction; 0.5 mixing and stir ,～2.0 parts of graphene oxides and 0.2～1.0 part of vitriol oil be warming up to 60～75 ℃; Insulation and ultrasonication 1～1.5 hour obtain graphene oxide modification allyl polyethenoxy ether;
3) in graphene oxide modification allyl polyethenoxy ether, add 1.72～5.16 parts of methylacrylic acids by mass fraction again, 0.16～0.95 part of methylpropene sodium sulfonate, 0.02～0.08 part of Resorcinol and 40～70 parts of deionized waters also continue ultrasonication and obtained mixed monomer solution in 0.5～1.0 hour;
4) 30～40 parts of deionized waters are added in the reaction kettle; Drip mixed monomer solution and initiator solution that step 3) is processed when being warming up to 80～90 ℃ respectively, the dropping time of mixed monomer solution is 1.0～1.5 hours, and the dropping time of initiator solution is 1.5～2.0 hours; Insulation reaction is 2.5～3 hours behind reinforced the finishing; Be cooled to 45 ℃, regulate pH=7.0, promptly get and strengthen the toughening type poly carboxylic acid series water reducer with sodium hydroxide solution.
2. the preparation method of enhancing toughening type poly carboxylic acid series water reducer according to claim 1 is characterized in that: the granularity of described Graphite Powder 99＜30 micron.
3. the preparation method of enhancing toughening type poly carboxylic acid series water reducer according to claim 1 is characterized in that: described vitriol oil massfraction is 98%.
4. the preparation method of enhancing toughening type poly carboxylic acid series water reducer according to claim 1 is characterized in that: described initiator solution is by mass fraction 0.2～0.4 part of ammonium persulphate to be dissolved in 20～30 parts of deionized waters to process.
5. the preparation method of enhancing toughening type poly carboxylic acid series water reducer according to claim 1 is characterized in that: the massfraction of described sodium hydroxide solution is 25%.
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