CN102604005B - A preparation method of reinforced and toughened polycarboxylate water reducer - Google Patents
A preparation method of reinforced and toughened polycarboxylate water reducer Download PDFInfo
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Abstract
本发明涉及一种增强增韧型聚羧酸系减水剂的制备方法。其方法是用浓硫酸和高锰酸钾对石墨粉进行氧化后进行超声波分离，得到了结构上含有羧基、羟基、环氧基等的氧化石墨烯，再在超声波的作用下使氧化石墨烯与烯丙基聚氧乙烯醚进行酯化反应。然后在过硫酸铵的引发下，与甲基丙烯酸和甲基丙烯磺酸钠进行自由基共聚合反应，得到一种具有增强增韧效果的聚羧酸系减水剂。本发明方法的创新之处在于通过氧化、分离、酯化和自由基共聚反应把氧化石墨烯结构引入到聚羧酸系减水剂分子中，除过所得减水剂的高减水率导致混凝土强度提高外，石墨烯本身也对混凝土具有增强增韧的效果。The invention relates to a preparation method of a reinforced and toughened polycarboxylate water reducer. The method is to use concentrated sulfuric acid and potassium permanganate to oxidize graphite powder and then perform ultrasonic separation to obtain graphene oxide containing carboxyl, hydroxyl, epoxy groups, etc. in the structure, and then make graphene oxide and Allyl polyoxyethylene ether undergoes esterification reaction. Then, under the initiation of ammonium persulfate, carry out free radical copolymerization reaction with methacrylic acid and sodium methacryl sulfonate to obtain a polycarboxylate water reducer with strengthening and toughening effect. The innovation of the method of the present invention is that the graphene oxide structure is introduced into the polycarboxylate water reducer molecules through oxidation, separation, esterification and free radical copolymerization, and the high water reducing rate of the obtained water reducer leads to concrete In addition to improving the strength, graphene itself also has the effect of strengthening and toughening concrete.
Description
Technical field
The invention belongs to the technical field of concrete additives in fine chemistry industry, be specifically related to a kind of preparation method that can increase the poly carboxylic acid series water reducer of concrete strength and toughness.
Background technology
Concrete is still the topmost material of construction in the world today, a large amount of cement of concrete need of production, sandstone etc., and these raw-material preparation process need to consume a large amount of natural resources and energy resources, also can produce huge environmental pollution simultaneously.In the today that reduces resource consumption, reduces energy consumption 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 the consumptions such as concrete and cement, and therefore, the additive that research and development can improve concrete strength has been subject to attention both domestic and external.The main method that improves at present concrete strength is to add to have the admixture that increases concrete strength, and this is also the focus of domestic and international research.
Graphite is the facile material of a kind of appearance, it is to be stacked by the plane carbon atom of arranging with honeycomb-patterned ordered from level to level to form, reactive force between layers is mainly weak Van der Waals force, peels off into thinner graphite flake layer than being easier to, and is exactly Graphene if graphite is stripped from into individual layer.By the functional modification to Graphene, can prepare the graphene nano material after 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, individual layer bi-dimensional cellular shape crystalline network for the formation of carbon atom close-packed arrays, have huge specific surface area and excellent mechanical property, wide material sources and the environmentally safe of while graphite, therefore, in use graphene oxide modified polycarboxylic acid based water reducer, very large prospect will be arranged.
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 concrete mechanical property and weather resistance.
For achieving the above object, the technical solution used in the present invention 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 ℃, mix the rear 18 parts of potassium permanganate that slowly add, at room temperature reacted 10 hours, slowly add 200 parts of deionized waters, be warming up to 68 ℃ and continue reaction 4 hours, then drip the superoxol of 20 parts of massfractions 30%, ultrasonic wave was disperseed after 30 minutes, centrifuging, repetitive scrubbing is removed sulfuric acid, the dry graphene oxide that gets under 60 ℃;
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) add 1.72～5.16 parts of methacrylic acids by mass fraction in graphene oxide modification allyl polyethenoxy ether 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 reactor, drip respectively step 3 when being warming up to 80～90 ℃) mixed monomer solution and the initiator solution made, the time for adding of hybrid monomers solution is 1.0～1.5 hours, the time for adding of initiator solution is 1.5～2.0 hours, reinforced complete rear insulation reaction 2.5～3 hours, be cooled to 45 ℃, regulate pH=7.0 with sodium hydroxide solution, namely get enhancing toughening type poly carboxylic acid series water reducer.
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 make.
The massfraction of described sodium hydroxide solution is 25%.
The present invention carries out carrying out ultrasonic wave after oxidation with the vitriol oil and potassium permanganate to Graphite Powder 99 to separate, obtained containing the graphene oxide of carboxyl, hydroxyl, epoxy group(ing) etc. on the structure, then made graphene oxide and allyl polyethenoxy ether carry out esterification under hyperacoustic effect.Then carry out free radical copolymerization with methacrylic acid and methylpropene sodium sulfonate under the effect of initiator, obtain having the poly carboxylic acid series water reducer that strengthens toughening effect.By oxidation, separation, esterification and free radicals copolymerization reaction, the graphene oxide structure is incorporated in the poly carboxylic acid series water reducer molecule, except 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 respectively 4.8%, 6.6% and 9.6%, and ultimate compression strength improves respectively 4.5%, 6.2% and 11.3%.
Description of drawings
Fig. 1 is synthetic route chart of the present invention.
Embodiment
Below in conjunction with accompanying drawing, the present invention is described in further detail.
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 rear 18 parts of potassium permanganate that slowly add, at room temperature reacted 10 hours, slowly add 200 parts of deionized waters, be warming up to 68 ℃ and continue reaction 4 hours, then drip the superoxol of 20 parts of massfractions 30%, ultrasonic wave was disperseed after 30 minutes, centrifuging, repetitive scrubbing is removed sulfuric acid, the dry graphene oxide that gets under 60 ℃;
2) get 20 parts of allyl polyethenoxy ethers by mass fraction, 0.5 part graphene oxide and 0.2 part of massfraction are 98% the vitriol oil to be mixed and stirs and be warming up to 60 ℃, insulation and ultrasonication 1 hour obtain graphene oxide modification allyl polyethenoxy ether;
3) add 1.72 parts of methacrylic acids by mass fraction in graphene oxide modification allyl polyethenoxy ether again, 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 reactor, drip respectively step 3 when being warming up to 80 ℃) mixed monomer solution and the initiator solution made, the time for adding of hybrid monomers solution is 1 hour, the time for adding of initiator solution is 1.6 hours, reinforced complete rear insulation reaction 2.5 hours, being cooled to 45 ℃, is 25% sodium hydroxide solution adjusting pH=7.0 with massfraction, namely 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 make.
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 rear 18 parts of potassium permanganate that slowly add, at room temperature reacted 10 hours, slowly add 200 parts of deionized waters, be warming up to 68 ℃ and continue reaction 4 hours, then drip the superoxol of 20 parts of massfractions 30%, ultrasonic wave was disperseed after 30 minutes, centrifuging, repetitive scrubbing is removed sulfuric acid, the dry graphene oxide that gets under 60 ℃;
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) add 2.58 parts of methacrylic acids by mass fraction in graphene oxide modification allyl polyethenoxy ether again, 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 reactor, drip respectively step 3 when being warming up to 82 ℃) mixed monomer solution and the initiator solution made, the time for adding of hybrid monomers solution is 1.3 hours, the time for adding of initiator solution is 1.5 hours, reinforced complete rear insulation reaction 3 hours, being cooled to 45 ℃, is 25% sodium hydroxide solution adjusting pH=7.0 with massfraction, namely 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 make.
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 rear 18 parts of potassium permanganate that slowly add, at room temperature reacted 10 hours, slowly add 200 parts of deionized waters, be warming up to 68 ℃ and continue reaction 4 hours, then drip the superoxol of 20 parts of massfractions 30%, ultrasonic wave was disperseed after 30 minutes, centrifuging, repetitive scrubbing is removed sulfuric acid, the dry graphene oxide that gets under 60 ℃;
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) add 3.44 parts of methacrylic acids by mass fraction in graphene oxide modification allyl polyethenoxy ether again, 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 reactor, drip respectively step 3 when being warming up to 84 ℃) mixed monomer solution and the initiator solution made, the time for adding of hybrid monomers solution is 1.3 hours, the time for adding of initiator solution is 1.5 hours, reinforced complete rear insulation reaction 2.6 hours, being cooled to 45 ℃, is 25% sodium hydroxide solution adjusting pH=7.0 with massfraction, namely 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 make.
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 rear 18 parts of potassium permanganate that slowly add, at room temperature reacted 10 hours, slowly add 200 parts of deionized waters, be warming up to 68 ℃ and continue reaction 4 hours, then drip the superoxol of 20 parts of massfractions 30%, ultrasonic wave was disperseed after 30 minutes, centrifuging, repetitive scrubbing is removed sulfuric acid, the dry graphene oxide that gets under 60 ℃;
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) add 5.16 parts of methacrylic acids by mass fraction in graphene oxide modification allyl polyethenoxy ether again, 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 reactor, drip respectively step 3 when being warming up to 86 ℃) mixed monomer solution and the initiator solution made, the time for adding of hybrid monomers solution is 1.5 hours, the time for adding of initiator solution is 2.0 hours, reinforced complete rear insulation reaction 2.7 hours, being cooled to 45 ℃, is 25% sodium hydroxide solution adjusting pH=7.0 with massfraction, namely 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 make.
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 rear 18 parts of potassium permanganate that slowly add, at room temperature reacted 10 hours, slowly add 200 parts of deionized waters, be warming up to 68 ℃ and continue reaction 4 hours, then drip the superoxol of 20 parts of massfractions 30%, ultrasonic wave was disperseed after 30 minutes, centrifuging, repetitive scrubbing is removed sulfuric acid, the dry graphene oxide that gets under 60 ℃;
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) add 3.44 parts of methacrylic acids by mass fraction in graphene oxide modification allyl polyethenoxy ether again, 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 reactor, drip respectively step 3 when being warming up to 88 ℃) mixed monomer solution and the initiator solution made, the time for adding of hybrid monomers solution is 2.0 hours, the time for adding of initiator solution is 1.5 hours, reinforced complete rear insulation reaction 2.8 hours, being cooled to 45 ℃, is 25% sodium hydroxide solution adjusting pH=7.0 with massfraction, namely 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 make.
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 rear 18 parts of potassium permanganate that slowly add, at room temperature reacted 10 hours, slowly add 200 parts of deionized waters, be warming up to 68 ℃ and continue reaction 4 hours, then drip the superoxol of 20 parts of massfractions 30%, ultrasonic wave was disperseed after 30 minutes, centrifuging, repetitive scrubbing is removed sulfuric acid, the dry graphene oxide that gets under 60 ℃;
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) add 4.3 parts of methacrylic acids by mass fraction in graphene oxide modification allyl polyethenoxy ether again, 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 reactor, drip respectively step 3 when being warming up to 90 ℃) mixed monomer solution and the initiator solution made, the time for adding of hybrid monomers solution is 1.4 hours, the time for adding of initiator solution is 1.8 hours, reinforced complete rear insulation reaction 3 hours, being cooled to 45 ℃, is 25% sodium hydroxide solution adjusting pH=7.0 with massfraction, namely 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 make.
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| CN112812239B (en) * | 2021-01-07 | 2023-08-25 | 青海省兴利公路桥梁工程有限公司 | Preparation process of high-performance polycarboxylate water reducer applied to concrete |
| CN113929343B (en) * | 2021-10-26 | 2023-05-30 | 浙江和业科技有限公司 | Method for preparing polycarboxylate water reducer by using vinyl polyoxyethylene ether |
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