CN103613307A - Slump type polycarboxylate superplasticizer and preparation method thereof - Google Patents

Slump type polycarboxylate superplasticizer and preparation method thereof Download PDF

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Publication number
CN103613307A
CN103613307A CN201310598234.6A CN201310598234A CN103613307A CN 103613307 A CN103613307 A CN 103613307A CN 201310598234 A CN201310598234 A CN 201310598234A CN 103613307 A CN103613307 A CN 103613307A
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weight
carboxylic acid
reducing agent
slump
water reducing
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CN201310598234.6A
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CN103613307B (en
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马保国
代柱端
谭洪波
汪杰
李相国
蹇守卫
黄健
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Wuhan University of Technology WUT
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Wuhan University of Technology WUT
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Abstract

The invention relates to a slump type polycarboxylate superplasticizer and a preparation method thereof. The molecular weight of the slump type polycarboxylate superplasticizer is 40000-65000, and the structural formula of the slump type polycarboxylate superplasticizer is shown as a formula (I), wherein m is 40-60, n is 45-70, k is 20-30, p is 10-30, t is 60-100. The slump type polycarboxylate superplasticizer and the preparation method thereof disclosed by the invention has the advantages that hydroxyethyl acrylate is introduced into a molecular structure and is hydrolyzed into carboxylic acid and alcohol in an alkaline environment, wherein a carboxylic acid group can play roles in delayed coagulation and slump retaining, and an alcoholic hydroxyl group can play a role in delayed coagulation; maleic anhydride is introduced into the molecular structure and can be hydrolyzed into two -COOH which can be subjected to complexing together with Ca<2+>, thereby delaying the hydration of cement; the temperature of synthesis reaction is low, the synthesis process is simple, the synthesis is easy; the slump retaining effect is obvious and the influence caused by weather is less; when being used together with other additives, the slump type polycarboxylate superplasticizer can be well compatible with the other additives.

Description

Collapse protective poly-carboxylic acid water reducing agent and preparation method thereof
Technical field
The invention belongs to additive for building material field, be specifically related to a kind of collapse protective poly-carboxylic acid water reducing agent and preparation method thereof.
Background technology
Since the sixties in 20th century, there are three kinds of high efficiency water reducing agents in foreign market, they are respectively benzene sulfonate formaldehyde condensation products, polycyclic aromatic hydrocarbon sulfonate formaldehyde condensation products and condensate of melamine sulfonate and formaldehyde, have brought thus the fast development of high efficiency water reducing agent exploitation with research.The polycarboxylic acid series high efficiency water reducing agent that polyacrylate and graft copolymer thereof be representative of take the beginning of the nineties develops rapidly, and becomes the developing direction of 21 century high efficiency water reducing agent.In Practical Project, because the chemical composition of cement is different with firing process, the difference of the raw-material quality height difference of sandstone and construction environment (temperature and humidity etc.), causes the consistency variation of Water-reducing Admixtures To Cements, thereby reduce the concrete slump.The initial slump and Slump Time losing of Large directly have influence on concrete pumpability, mobility and water-retentivity.The slump retaining of improvement polycarboxylate water-reducer, will affect the workability of high performance concrete.
The chemical structure of general formula of common polycarboxylic acid series high efficiency water reducing agent is as follows, wherein M 1and M 2represent H, alkalimetal ion; M 3represent H, basic metal ammonium ion or organic amine.The molecular structure of polycarboxylate water-reducer belongs to comb shaped structure, and the functional groups such as the carboxylic acid group on its side chain and sulfonic group can make cement granules high dispersing, thereby delay hydrated cementitious.The electric density and the zeta-potential that increase in addition polycarboxylate water-reducer molecular chain can improve its dispersiveness, but so, it is too fast in the absorption of cement granules, reduces on the contrary water-reducing effect.In polycarboxylate water-reducer, carboxylic acid group and sulfonic group ratio are high, are easy to be adsorbed on particle surface, make concrete flowability retention meet the requirement of pumping; But surpass, mix and can make fresh concrete occur serious bleeding segregation phenomenon, affecting concrete application property and weather resistance.
The method that improves at present function of slump protection mainly contains following several: 1. use retardant and water reducer pair to mix, but excessive use retardant can affect construction speed and construction quality; 2. add water reducer two times, although can effectively increase the concrete slump, also can cause the super of admixture to be mixed simultaneously; 3. adopt multiple water reducer composite, but just sometimes can solve the problem of slump-loss.
Contriver discloses a kind of preparation method of polycarboxylic acid high slump retaining agent in CN102093521A patent: adopt maleic anhydride and poly-second diester double esterification legal system for cross-linking monomer, with the copolymerization in redox system of macromole unsaturated polyether, generating portion is crosslinked.But esterification yield is not high, and environmental protection not.
Contriver discloses a kind of slow-release type polycarboxylate slump-retaining agent and preparation method thereof in CN102390950 patent: adopt unsaturated carboxylic acid polyoxyethylene glycol monoesters, unsaturated polyalkylene oxide base ether monoesters, unsaturated monocarboxylic acid and derivatives monomer thereof and unsaturated thiazolinyl sulfonic acid and sodium salt copolymerization thereof to mix.Can effectively solve sandstone material that silt content is large and the compatibility problem of water reducer, but its effectiveness is subject to the impact of temperature and pH larger.
Contriver discloses a kind of preparation method of polycarboxylic acid slump retaining agent in CN102558454A patent; By tail washings, unsaturated polyether and the acrylic acid copolymer derivative of producing propenal, formed.Though can reduce the production cost of slump retaining agent, but it can not stop the absorption of the layered porous internal structure of clay, show when sandstone silt content is high, protect the effect of collapsing undesirable.
By research, find, the loss of the slump depends primarily on the speed that high efficiency water reducing agent dispersive ability reduces.The unstable of cement slurry is that they have large interfacial energy, thereby can automatically reduce interface, particle coalescent trend mutually; Collision on the other hand, because dispersed phase particles is little, is difficult to sink, once can be assembled in aggravation.Mix after high efficiency water reducing agent, the hydrophobic grouping oriented adsorption of water reducer, in cement particle surface, forms the adsorption layer of highfield, and cement particle is disperseed, thereby hinders or destroy the formation of the solidifying flocculation structure of cement cementitious body.High efficiency water reducing agent is because molecular configuration is complicated, sterically hindered to absorption generation in addition, suppresses the adsorptive capacity of cement for superplasticizer, thereby makes the unlikely fast-descending of dispersive ability.
Summary of the invention
Technical problem to be solved by this invention be for above-mentioned prior art, provide a kind of production technique simple, can with multiple composition of concrete admixture is used, good to the consistency of cement, the high guarantor of low-dosage is collapsed polycarboxylate water-reducer and preparation method thereof.
The present invention solves the problems of the technologies described above adopted technical scheme: collapse protective poly-carboxylic acid water reducing agent, its molecular weight is 40000~65000, general structure as shown in the formula:
In formula: m=40~60, n=45~70, k=20~30, p=10~30, t=60~100.
The preparation method of described collapse protective poly-carboxylic acid water reducing agent, it is characterized in that including following steps: TPEG, vinylbenzene, methacrylic disulfonate acid and maleic anhydride are dropped in reactor simultaneously, add water, above-mentioned each material is totally 100 weight parts, wherein the mass ratio of water and TPEG is 0.6, stirs and is heated to 50~70 ℃, insulation, start to drip Hydroxyethyl Acrylate solution 6~9 weight parts of massfraction 40~60%, 2~3h drips completely simultaneously; Initiator solution 0.8~1.5 weight part of massfraction 1~4%, 2~3h drips completely and molecular-weight adjusting agent solution 0.08~0.36 weight part of massfraction 2~3%, 3~4h drips completely, wait to dropwise, insulation 1~2h, with alkali, regulate pH=6~8, obtain collapse protective poly-carboxylic acid water reducing agent solution.
Press such scheme, TPEG: vinylbenzene: methacrylic disulfonate acid: the mass ratio of maleic anhydride is 1:0.2~0.4:0.1~0.2:0.16~0.25.
Press such scheme, described initiator is the mixture of ammonium persulphate and Potassium Persulphate, and its mass ratio is 1:1~7.
Press such scheme, described molecular weight regulator is the mixture of Thiovanic acid and β-mercaptopropionic acid, and its mass ratio is 1:1~5.
Building-up reactions equation of the present invention is as follows:
Compare with existing collapse protection type water reducer, the invention has the advantages that:
A. the Hydroxyethyl Acrylate of introducing in molecular structure is hydrolyzed to Carboxylic acid and alcohol under alkaline environment, and wherein carboxylic acid group can play slow setting and guarantor's effect of collapsing, and alcoholic extract hydroxyl group can play delayed coagulation;
B. the maleic anhydride of introducing in molecular structure can be hydrolyzed to two-COOH under alkaline environment, can complexing Ca 2+, can effectively delay hydrated cementitious;
C. the sulfonic acid group of introducing in molecular structure, can preferentially disperse cement granules, delays hydrated cementitious;
D. the temperature of building-up reactions is lower, and synthesis technique is simple, is easy to synthesize;
E. protect the successful that collapses, the impact of climate is little, and while being used in conjunction with other admixtures, consistency is good.
Embodiment
For illustrating further content of the present invention, exemplify especially following examples the present invention is described in further detail.Embodiment provides in the mode of explanation, but is never only confined to content of the present invention.Protection scope of the present invention is as the criterion with claims.The present invention is by indexs such as the test slump and water-reducing rates, and control commercial product and each embodiment products obtained therefrom are evaluated.
Collapse protective poly-carboxylic acid water reducing agent, its molecular weight is 40000~65000, general structure as shown in the formula:
In formula: m=40~60, n=45~70, k=20~30, p=10~30, t=60~100.
Embodiment 1
Take TPEG45 weight part, vinylbenzene 12 weight parts, methacrylic disulfonate acid 6 weight parts, maleic anhydride 10 weight parts, join wiring solution-forming in 27 weight parts waters, be heated with stirring to 70 ℃ after constant temperature; Drip A simultaneously and expect that 6 weight parts, B expect that 0.8 weight part and C expect 0.08 weight part, A material and B material drip completely at 2h, and C material drips completely at 3h; Wherein A material is the Hydroxyethyl Acrylate solution of massfraction 50%; B material is the initiator solution of massfraction 2.5%, and initiator is the mixture of ammonium persulphate and Potassium Persulphate, and its mass ratio is 1:3; C material is the molecular-weight adjusting agent solution of massfraction 2.5%, and C material is the mixture of Thiovanic acid with β-mercaptopropionic acid, and its mass ratio is 1:2, is incubated 2h, and hydro-oxidation sodium tune pH=8 obtains concentration and be 40% collapse protective poly-carboxylic acid water reducing agent solution.
Embodiment 2
Take TPEG45 weight part, vinylbenzene 14 weight parts, methacrylic disulfonate acid 5 weight parts, maleic anhydride 9 weight parts, join wiring solution-forming in 27 weight parts waters, be heated with stirring to 70 ℃ after constant temperature; Drip A simultaneously and expect that 6 weight parts, B expect that 0.8 weight part and C expect 0.08 weight part, A material and B material drip completely at 2h, and C material drips completely at 3h; Wherein A material is the Hydroxyethyl Acrylate solution of massfraction 50%; B material is the initiator solution of massfraction 2.5%, and initiator is the mixture of ammonium persulphate and Potassium Persulphate, and its mass ratio is 1:3; C material is the molecular-weight adjusting agent solution of massfraction 2.5%, and C material is the mixture of Thiovanic acid with β-mercaptopropionic acid, and its mass ratio is 1:2, is incubated 2h, and hydro-oxidation sodium tune pH=8 obtains concentration and be 40% collapse protective poly-carboxylic acid water reducing agent solution.
Embodiment 3
Take TPEG45 weight part, vinylbenzene 12 weight parts, methacrylic disulfonate acid 6 weight parts, maleic anhydride 10 weight parts, join wiring solution-forming in 27 weight parts waters, be heated with stirring to 50 ℃ after constant temperature; Drip A simultaneously and expect that 6 weight parts, B expect that 0.8 weight part and C expect 0.08 weight part, A material and B material drip completely at 2h, and C material drips completely at 3h; Wherein A material is the Hydroxyethyl Acrylate solution of massfraction 50%; B material is the initiator solution of massfraction 2.5%, and initiator is the mixture of ammonium persulphate and Potassium Persulphate, and its mass ratio is 1:3; C material is the molecular-weight adjusting agent solution of massfraction 2.5%, and C material is the mixture of Thiovanic acid with β-mercaptopropionic acid, and its mass ratio is 1:2, is incubated 2h, and hydro-oxidation sodium tune pH=8 obtains concentration and be 40% collapse protective poly-carboxylic acid water reducing agent solution.
Embodiment 4
Take TPEG45 weight part, vinylbenzene 12 weight parts, methacrylic disulfonate acid 6 weight parts, maleic anhydride 10 weight parts, join wiring solution-forming in 27 weight parts waters, be heated with stirring to 70 ℃ after constant temperature; Drip A simultaneously and expect that 9 weight parts, B expect that 1.5 weight parts and C expect 0.36 weight part, A material and B material drip completely at 2h, and C material drips completely at 3h; Wherein A material is the Hydroxyethyl Acrylate solution of massfraction 50%; B material is the initiator solution of massfraction 2.5%, and initiator is the mixture of ammonium persulphate and Potassium Persulphate, and its mass ratio is 1:3; C material is the molecular-weight adjusting agent solution of massfraction 2.5%, and C material is the mixture of Thiovanic acid with β-mercaptopropionic acid, and its mass ratio is 1:2, is incubated 2h, and hydro-oxidation sodium tune pH=8 obtains concentration and be 40% collapse protective poly-carboxylic acid water reducing agent solution.
Embodiment 5
Take TPEG45 weight part, vinylbenzene 12 weight parts, methacrylic disulfonate acid 6 weight parts, maleic anhydride 10 weight parts, join wiring solution-forming in 27 weight parts waters, be heated with stirring to 70 ℃ after constant temperature; Drip A simultaneously and expect that 6 weight parts, B expect that 0.8 weight part and C expect 0.08 weight part, A material and B material drip completely at 2h, and C material drips completely at 3h; Wherein A material is the Hydroxyethyl Acrylate solution of massfraction 50%; B material is the initiator solution of massfraction 2.5%, and initiator is the mixture of ammonium persulphate and Potassium Persulphate, and its mass ratio is 1:6; C material is the molecular-weight adjusting agent solution of massfraction 2.5%, and C material is the mixture of Thiovanic acid with β-mercaptopropionic acid, and its mass ratio is 1:2, is incubated 2h, and hydro-oxidation sodium tune pH=8 obtains concentration and be 40% collapse protective poly-carboxylic acid water reducing agent solution.
Embodiment 6
Take TPEG45 weight part, vinylbenzene 12 weight parts, methacrylic disulfonate acid 6 weight parts, maleic anhydride 10 weight parts, join wiring solution-forming in 27 weight parts waters, be heated with stirring to 70 ℃ after constant temperature; Drip A simultaneously and expect that 6 weight parts, B expect that 0.8 weight part and C expect 0.08 weight part, A material and B material drip completely at 2h, and C material drips completely at 3h; Wherein A material is the Hydroxyethyl Acrylate solution of massfraction 50%; B material is the initiator solution of massfraction 2.5%, and initiator is the mixture of ammonium persulphate and Potassium Persulphate, and its mass ratio is 1:3; C material is the molecular-weight adjusting agent solution of massfraction 2.5%, and C material is the mixture of Thiovanic acid with β-mercaptopropionic acid, and its mass ratio is 1:5, is incubated 2h, and hydro-oxidation sodium tune pH=8 obtains concentration and be 40% collapse protective poly-carboxylic acid water reducing agent solution.
Embodiment 7
Take TPEG45 weight part, vinylbenzene 12 weight parts, methacrylic disulfonate acid 6 weight parts, maleic anhydride 10 weight parts, join wiring solution-forming in 27 weight parts waters, be heated with stirring to 70 ℃ after constant temperature; Drip A simultaneously and expect that 6 weight parts, B expect that 0.8 weight part and C expect 0.08 weight part, A material and B material drip completely at 2h, and C material drips completely at 3h; Wherein A material is the Hydroxyethyl Acrylate solution of massfraction 50%; B material is the initiator solution of massfraction 2.5%, and initiator is the mixture of ammonium persulphate and Potassium Persulphate, and its mass ratio is 1:3; C material is the molecular-weight adjusting agent solution of massfraction 2.5%, and C material is the mixture of Thiovanic acid with β-mercaptopropionic acid, and its mass ratio is 1:2, is incubated 1h, and hydro-oxidation sodium tune pH=8 obtains concentration and be 40% collapse protective poly-carboxylic acid water reducing agent solution.
Embodiment 8
Take TPEG45 weight part, vinylbenzene 12 weight parts, methacrylic disulfonate acid 6 weight parts, maleic anhydride 10 weight parts, join wiring solution-forming in 27 weight parts waters, be heated with stirring to 70 ℃ after constant temperature; Drip A simultaneously and expect that 6 weight parts, B expect that 0.8 weight part and C expect 0.08 weight part, A material and B material drip completely at 2h, and C material drips completely at 3h; Wherein A material is the Hydroxyethyl Acrylate solution of massfraction 50%; B material is the initiator solution of massfraction 2.5%, and initiator is the mixture of ammonium persulphate and Potassium Persulphate, and its mass ratio is 1:3; C material is the molecular-weight adjusting agent solution of massfraction 2.5%, and C material is the mixture of Thiovanic acid with β-mercaptopropionic acid, and its mass ratio is 1:2, is incubated 2h, and hydro-oxidation sodium tune pH=6 obtains concentration and be 40% collapse protective poly-carboxylic acid water reducing agent solution.
Product to above 8 embodiment is evaluated
Above 8 example products are combined into solution (numbering 1,2,3,4,5,6,7,8) with LonS-P polycarboxylate water-reducer 1:4 respectively, and take poly carboxylic acid LonS-P product as contrast sample, according to GB8076-2008, carry out concrete application performance and water-reducing rate experiment.Wherein use the secondary ash 80g of China new P.O42.5 cement 200g ,Yang Luo power plant, the new S95 level breeze 80g of China, sand 790g, stone 1080g, water 170g.
The above example 1~8 of contrast can be found out, after the collapse protective poly-carboxylic acid water reducing agent that interpolation the method for the invention makes, concrete protect plasticity can significantly improve, although water-reducing rate slightly reduces to be improved greatly integral working, has good use value.

Claims (5)

1. collapse protective poly-carboxylic acid water reducing agent, its molecular weight is 40000~65000, general structure as shown in the formula:
In formula: m=40~60, n=45~70, k=20~30, p=10~30, t=60~100.
2. the preparation method of collapse protective poly-carboxylic acid water reducing agent claimed in claim 1, it is characterized in that including following steps: TPEG, vinylbenzene, methacrylic disulfonate acid and maleic anhydride are dropped in reactor simultaneously, add water, above-mentioned each material is totally 100 weight parts, wherein the mass ratio of water and TPEG is 0.6, stirs and is heated to 50~70 ℃, insulation, start to drip Hydroxyethyl Acrylate solution 6~9 weight parts of massfraction 40~60%, 2~3h drips completely simultaneously; Initiator solution 0.8~1.5 weight part of massfraction 1~4%, 2~3h drips completely and molecular-weight adjusting agent solution 0.08~0.36 weight part of massfraction 2~3%, 3~4h drips completely, wait to dropwise, insulation 1~2h, with alkali, regulate pH=6~8, obtain collapse protective poly-carboxylic acid water reducing agent solution.
3. the preparation method of collapse protective poly-carboxylic acid water reducing agent according to claim 2, is characterized in that TPEG: vinylbenzene: methacrylic disulfonate acid: the mass ratio of maleic anhydride is 1:0.2~0.4:0.1~0.2:0.16~0.25.
4. according to the collapse protective poly-carboxylic acid water reducing agent preparation method described in claim 2 or 3, it is characterized in that described initiator is the mixture of ammonium persulphate and Potassium Persulphate, its mass ratio is 1:1~7.
5. according to the preparation method of the collapse protective poly-carboxylic acid water reducing agent described in claim 2 or 3, it is characterized in that described molecular weight regulator is the mixture of Thiovanic acid and β-mercaptopropionic acid, its mass ratio is 1:1~5.
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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104140220A (en) * 2014-07-28 2014-11-12 武汉理工大学 Concrete slump compensating agent and preparation method and application thereof
CN104672401A (en) * 2015-03-13 2015-06-03 武汉理工大学 Preparation method for slump retaining agent for polycarboxylate superplasticizer
CN104860567A (en) * 2015-05-12 2015-08-26 武汉理工大学 Disperse thickening agent for phosphorus gypsum based self-leveling mortar and preparation method
CN105622853A (en) * 2015-12-24 2016-06-01 江苏苏博特新材料股份有限公司 Preparing method of mud-blocking type water reducing agent
CN106477962A (en) * 2016-10-27 2017-03-08 重庆绿恒环保科技有限公司 A kind of cement base pervious concrete additive
CN108484839A (en) * 2018-03-23 2018-09-04 刘翠芬 A kind of amphipathic carboxylic dispersants and preparation method thereof

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CN102603996A (en) * 2012-02-28 2012-07-25 武汉理工大学 Ether type polycarboxylic acid slump retaining agent and preparation method thereof
CN102924669A (en) * 2011-08-10 2013-02-13 广州泰祥混凝土外加剂有限公司 Preparation method of polycarboxylate superplasticizer

Patent Citations (2)

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CN102924669A (en) * 2011-08-10 2013-02-13 广州泰祥混凝土外加剂有限公司 Preparation method of polycarboxylate superplasticizer
CN102603996A (en) * 2012-02-28 2012-07-25 武汉理工大学 Ether type polycarboxylic acid slump retaining agent and preparation method thereof

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104140220A (en) * 2014-07-28 2014-11-12 武汉理工大学 Concrete slump compensating agent and preparation method and application thereof
CN104672401A (en) * 2015-03-13 2015-06-03 武汉理工大学 Preparation method for slump retaining agent for polycarboxylate superplasticizer
CN104860567A (en) * 2015-05-12 2015-08-26 武汉理工大学 Disperse thickening agent for phosphorus gypsum based self-leveling mortar and preparation method
CN105622853A (en) * 2015-12-24 2016-06-01 江苏苏博特新材料股份有限公司 Preparing method of mud-blocking type water reducing agent
CN105622853B (en) * 2015-12-24 2017-11-24 江苏苏博特新材料股份有限公司 A kind of preparation method for hindering chamotte mould water reducer
CN106477962A (en) * 2016-10-27 2017-03-08 重庆绿恒环保科技有限公司 A kind of cement base pervious concrete additive
CN108484839A (en) * 2018-03-23 2018-09-04 刘翠芬 A kind of amphipathic carboxylic dispersants and preparation method thereof

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