CN102604005B - Preparation method of strengthening and toughening polycarboxylate water reducing agent - Google Patents
Preparation method of strengthening and toughening polycarboxylate water reducing agent Download PDFInfo
- Publication number
- CN102604005B CN102604005B CN 201210010918 CN201210010918A CN102604005B CN 102604005 B CN102604005 B CN 102604005B CN 201210010918 CN201210010918 CN 201210010918 CN 201210010918 A CN201210010918 A CN 201210010918A CN 102604005 B CN102604005 B CN 102604005B
- Authority
- CN
- China
- Prior art keywords
- parts
- hours
- graphene oxide
- water reducer
- carboxylic acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Landscapes
- Macromonomer-Based Addition Polymer (AREA)
- Polymerisation Methods In General (AREA)
- Carbon And Carbon Compounds (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
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 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.
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 ℃, 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.
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, it 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, it 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 make.
5. the preparation method of enhancing toughening type poly carboxylic acid series water reducer according to claim 1, it is characterized in that: the massfraction of described sodium hydroxide solution is 25%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201210010918 CN102604005B (en) | 2012-01-13 | 2012-01-13 | Preparation method of strengthening and toughening polycarboxylate water reducing agent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201210010918 CN102604005B (en) | 2012-01-13 | 2012-01-13 | Preparation method of strengthening and toughening polycarboxylate water reducing agent |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102604005A CN102604005A (en) | 2012-07-25 |
| CN102604005B true CN102604005B (en) | 2013-05-15 |
Family
ID=46521817
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201210010918 Active CN102604005B (en) | 2012-01-13 | 2012-01-13 | Preparation method of strengthening and toughening polycarboxylate water reducing agent |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102604005B (en) |
Families Citing this family (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103058541A (en) * | 2013-01-22 | 2013-04-24 | 大连海事大学 | Application of graphene oxide as reinforcing agent of cement early strength |
| CN103242007B (en) * | 2013-05-22 | 2014-10-22 | 陕西科技大学 | Preparation method of graphene oxide modified polymer cement waterproof coating |
| CN103241983B (en) * | 2013-05-22 | 2014-07-16 | 陕西科技大学 | Preparation method of graphene oxide modified polycarboxylic acid type water-reducer |
| CN103589197B (en) * | 2013-11-25 | 2014-11-26 | 桂林理工大学 | Method for preparing flexibilizer by adopting oxidized graphene and application thereof |
| CN104628294A (en) * | 2015-02-13 | 2015-05-20 | 陕西科技大学 | Graphene oxide based composite material for cement-based materials and preparation method thereof |
| CN105541210B (en) * | 2015-12-28 | 2017-09-15 | 四川碳世界科技有限公司 | A kind of graphene oxide concrete |
| CN106189680A (en) * | 2016-07-04 | 2016-12-07 | 沈阳化工大学 | A kind of building fire-resisting coating material and preparation method thereof |
| CN106478895B (en) * | 2016-10-09 | 2019-02-01 | 武汉工程大学 | A kind of compound polycarboxylate water-reducer of graphene oxide and preparation method thereof |
| CN107513137B (en) * | 2017-09-15 | 2020-05-05 | 恒信智能（天津）快速制造技术有限公司 | Method for preparing graphene photocuring resin nano material, pouring solution and pouring method |
| CN108084363A (en) * | 2017-12-28 | 2018-05-29 | 科之杰新材料集团有限公司 | A kind of preparation method of reinforcing type polycarboxylic acid water-reducing agent |
| CN108179418B (en) * | 2018-02-08 | 2024-02-20 | 广州超邦化工有限公司 | Preparation method of zinc-nickel alloy coating structure suitable for strong corrosion environment |
| CN108218279B (en) * | 2018-03-26 | 2019-01-22 | 白彤洲 | A kind of building trade cement water reducing agent and preparation method thereof containing graphene |
| CN111234130B (en) * | 2020-03-25 | 2023-08-29 | 安新县金运化工原料有限公司 | Mi's acid modified polycarboxylic acid high-efficiency water reducer and preparation method thereof |
| 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 |
| CN114349386B (en) * | 2021-12-28 | 2023-05-19 | 重庆建研科之杰新材料有限公司 | Concrete water reducer and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1655272A1 (en) * | 2004-11-04 | 2006-05-10 | Mapei S.p.A. | Superplasticizers for extending the workability of mortars |
| CN101024566A (en) * | 2007-01-29 | 2007-08-29 | 郭震 | Polycarboxylic acid series concrete composite water-proof agent and its preparing method |
| CN101357834A (en) * | 2008-08-22 | 2009-02-04 | 上海三瑞高分子材料有限公司 | High-early strength polyocarboxy acid superplasticiser |
| CN102093519A (en) * | 2010-12-06 | 2011-06-15 | 江苏汇迪建材有限公司 | Preparation method of mud-resistant type polycarboxylate superplasticizer |
-
2012
- 2012-01-13 CN CN 201210010918 patent/CN102604005B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1655272A1 (en) * | 2004-11-04 | 2006-05-10 | Mapei S.p.A. | Superplasticizers for extending the workability of mortars |
| CN101024566A (en) * | 2007-01-29 | 2007-08-29 | 郭震 | Polycarboxylic acid series concrete composite water-proof agent and its preparing method |
| CN101357834A (en) * | 2008-08-22 | 2009-02-04 | 上海三瑞高分子材料有限公司 | High-early strength polyocarboxy acid superplasticiser |
| CN102093519A (en) * | 2010-12-06 | 2011-06-15 | 江苏汇迪建材有限公司 | Preparation method of mud-resistant type polycarboxylate superplasticizer |
Non-Patent Citations (4)
| Title |
|---|
| "Polymeric Modification of Graphene through Esterification of Graphite Oxide and Poly(vinyl alcohol)";Horacio J. Salavagione et al;《Macromolecules》;20090813;第42卷(第17期);6331-6334 * |
| "聚羧酸系减水剂结构与分散性能研究进展";段建平 等;《混凝土》;20111231(第11期);59-63,66 * |
| Horacio J. Salavagione et al."Polymeric Modification of Graphene through Esterification of Graphite Oxide and Poly(vinyl alcohol)".《Macromolecules》.2009,第42卷(第17期),6331-6334. |
| 段建平 等."聚羧酸系减水剂结构与分散性能研究进展".《混凝土》.2011,(第11期),59-63,66. |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102604005A (en) | 2012-07-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102604005B (en) | Preparation method of strengthening and toughening polycarboxylate water reducing agent | |
| CN102358768B (en) | Modified ether polycarboxylic acid water reducing agent and preparation method thereof | |
| CN103183792B (en) | Preparation method of polycarboxylic water reducer | |
| CN103265201B (en) | Sorbitol modified polycarboxylate-type water reducing agent and synthetic method thereof | |
| CN103193425B (en) | High strength pumping anti-crack concrete prepared by slag aggregate and production method thereof | |
| CN103641370B (en) | Composite cement enhanced grinding aid containing amide polyamine polycarboxylic acids and preparation method therefor | |
| CN103803846A (en) | Mud-resistant and salt-resistant polycarboxylate superplasticizer and preparation method thereof | |
| CN103613308B (en) | Water-reducing polycarboxylic concrete slump retaining agent and preparation method thereof | |
| CN102503227A (en) | Early-strength polycarboxylic acid water reducing agent | |
| CN102351999A (en) | Method for preparing nanoparticle water reducing agent | |
| CN105645810A (en) | Early-strength polycarboxylate type high-performance water reducing agent and preparation method | |
| CN109232820B (en) | Method for preparing temperature response type comb-shaped structure polycarboxylic acid by end group functionalization | |
| CN104692701B (en) | A kind of normal temperature synthesis type polycarboxylate high performance water-reducing agent and preparation method | |
| CN112279675B (en) | Foam concrete based on high-stability foaming agent and preparation method thereof | |
| CN105271900A (en) | Polycarboxylate superplasticizer with super high early strength and preparation method of polycarboxylate superplasticizer | |
| CN105111383A (en) | Process for preparing high-performance polycarboxylic acid type water-reducing agent by combined macromonomers at normal temperature | |
| CN112851889A (en) | Preparation method of graphene oxide modified TPEG type polycarboxylate superplasticizer | |
| CN102503221B (en) | Cyclohexanol grafted polycarboxylic acid water reducing agent and preparation method thereof | |
| CN104151477A (en) | Preparation method of amphoteric polycarboxylate clay inhibitor | |
| CN104276782A (en) | Polyether type polycarboxylate superplasticizer | |
| CN104371075B (en) | A kind of preparation method of the polycarboxylate water-reducer of room temperature synthesis | |
| CN104478279A (en) | Multi-sulfonate type cement water reducing agent and preparation method thereof | |
| CN104892856B (en) | A kind of preparation method of polycarboxylate water-reducer | |
| CN105461251A (en) | Novel polycarboxylate superplasticizer and preparation method thereof | |
| CN102408528B (en) | Preparation method for polycarboxylic acid water reducer with strong adaptability |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20180720 Address after: 051430 Wangjiazhuang Village West Luancheng District Shijiazhuang city Hebei Province Patentee after: HEBEI SHENGTONG BUILDING MATERIALS TECHNOLOGY Co.,Ltd. Address before: 710016 Shaanxi Xi'an economic and Technological Development Zone, Fengcheng two road 10, Tiandi Times Square, the first building 2 unit 16 level 21616. Patentee before: Shanxi Huaqi UTS Intellectual Property Agency Co.,Ltd. Xi'an branch Effective date of registration: 20180720 Address after: 710016 Shaanxi Xi'an economic and Technological Development Zone, Fengcheng two road 10, Tiandi Times Square, the first building 2 unit 16 level 21616. Patentee after: Shanxi Huaqi UTS Intellectual Property Agency Co.,Ltd. Xi'an branch Address before: No. 1, Weiyang District university garden, Xi'an, Shaanxi Province, Shaanxi Patentee before: SHAANXI University OF SCIENCE & TECHNOLOGY |
|
| TR01 | Transfer of patent right |