CN100400458C - Lignins metro shield grouting additive and its preparation method - Google Patents

Lignins metro shield grouting additive and its preparation method Download PDF

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Publication number
CN100400458C
CN100400458C CNB2005100326558A CN200510032655A CN100400458C CN 100400458 C CN100400458 C CN 100400458C CN B2005100326558 A CNB2005100326558 A CN B2005100326558A CN 200510032655 A CN200510032655 A CN 200510032655A CN 100400458 C CN100400458 C CN 100400458C
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weight
shield grouting
mixtures
lignins
percent
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CN1654406A (en
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邱学青
楼宏铭
杨东杰
庞煜霞
郑大锋
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South China University of Technology SCUT
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South China University of Technology SCUT
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Abstract

The present invention relates to a lignin series admixture for subway shield grouting and a preparation method thereof. The preparation method uses 1000 percent by weight of modified lignosulphonate provided by the ZL98116516.8 patent, 20 to 200 percent by weight of crosslinking agent, 1 to 50 percent by weight of air entraining agent, 100 to 500 percent by weight of inorganic salt reinforcing agent and 10 to 50 percent by weight of water-soluble macromolecule polymer as raw materials to obtain a product by condensation reaction and physical formulation. The product of the present invention has better water reducing reinforced action and stabilization action for the subway shield grouting, and the grouting has proper setting time and smaller pumping resistance.

Description

Lignins metro shield grouting additive and preparation method thereof
Technical field
The present invention relates to a kind of mortar additive and preparation method thereof.Specifically be to be a kind of Lignins metro shield grouting additive that is applied to metro shield grouting of feedstock production with the modified lignin sulfonate.
Background technology
Subway has advantages such as freight volume is big, speed fast, pollution is few becomes one of chief city's vehicles.The constructing metro tunnel technology mainly contains drilling and blasting method, cut and cover method and shielding method etc.Shield construction is safer, automatization level is high, it is little that above ground structure is influenced, and has become the main method of subway work.
In the process in shielding method digging tunnel, because the external diameter of shield engine is bigger than the external diameter of tunnel duct piece, shield engine stays the annular space of 100~200mm between lining segment and natural soil layer (or rock stratum) by the back.For preventing land subsidence, need in annular space, inject slurry.Inject slurry and played effects such as support stratum, the stability of guaranteeing early stage pipe-plate lining and raising tunnel water proofing performance.
General shield grouting is made up of cement, flyash, wilkinite, sand, water and admixture.But for reaching pumping, the easily requirement of slip casting, shield grouting need adopt the slurry of high flowability.So greatly reduce stability of slurry, make the easy bleeding of slurry, segregation seriously, cause easy blocking pipe in the pumping process, often can not construct continuously, directly influence construction quality and construction speed.After slurry injected annular space, water layer appearred in segregation at the top, loses the supporting role to ground, and severe patient will directly jeopardize the safety of above ground structure, cause serious engineering accident.Therefore, all different with traditional ground slip casting and pump concrete, when having high flowability, the shield grouting material requirements also requires to have satisfactory stability, impermeability, ultimate compression strength and suitable time of coagulation etc.
Adding admixture is the important measures that improve the metro shield grouting performance.The admixture that uses mainly is the high efficiency water reducing agent that is applied to concrete works at present, as naphthalenesulfonate formaldehyde condensation compound high efficiency water reducing agent, condensate of melamine sulfonate and formaldehyde high efficiency water reducing agent, thionamic acid phenol formaldehyde (PF) condenses high efficiency water reducing agent etc.Though these high efficiency water reducing agents have good diminishing enhancement, and are poor to the stabilization of slip casting, slurry bleeding, segregation are serious, and time of coagulation is also short partially.Therefore, often cause pumping line to stop up, the layering of emanating after the slip casting causes land subsidence easily.Therefore traditional high efficiency water reducing agent can't satisfy the requirement of shield grouting at aspects such as stability and time of coagulation.
Sulfonated lignin are to use water reducer the earliest, just notice that sulfite cellulose and various concentrated solution can improve concrete flowability abroad as far back as early 1930s.But because Sulfite lignin have delayed coagulation, overdose uses and will cause concrete strength to reduce, even concrete takes place in non-sclerous phenomenon of long duration, uses to be restricted in concrete.Present patent application people is the main application and the Chinese invention patent (ZL98116516.8) of having authorized, adopts a kind of method of molecular radical design, with lignin sulfonate modified be high efficiency water reducing agent, widened the range of application of lignin water reducer.The patented product has following characteristics:
(1) adopt the method for molecular radical design to carry out chemical modification, the molecular weight of product is 60%~90% of a calcium lignin sulphonate; Wetting ability weakens, and hydrophobic nature increases.
(2) the surperficial physical and chemical performance of product improves.Micelle-forming concentration appears in solution, and is bigger than calcium lignin sulphonate in the adsorptive capacity of cement granules, and dispersed strong, latherability is littler than calcium lignin sulphonate.
(3) be applied in the concrete, not only the diminishing reinforced effects reaches the standard of high efficiency water reducing agent among the GB8076-87, and loss of slump is little, and concrete is wrapped up in slurry property, homogeneity is good.
Above-mentioned modified lignin sulfonate high efficiency water reducing agent is used for the contradiction that shield grouting has partly solved high flowability and stability, but its time of coagulation is long, stability yet need improve.
Summary of the invention
The purpose of patent of the present invention is on the basis of patent of invention (ZL98116516.8), with sulfonated lignin is the preparation method that main raw material provides a kind of Lignins metro shield grouting additive, solves the poor stability that exists in the present shield grouting, the easy stratified problem of emanating.
The present invention also aims to provide the Lignins metro shield grouting additive of described method preparation.
The preparation method of Lignins metro shield slurrying admixture of the present invention may further comprise the steps:
The modified lignin mahogany sulfonate concrete high efficiency water reducing agent that (1) 1000 weight part patent of invention (ZL98116516.8) is produced, be dissolved in 1000~2000 weight parts waters, be heated to 60~100 ℃ while stirring, add 20~200 weight part linking agents, carry out polycondensation 0.5~10h;
(2) add 1~50 weight part air entrapment agent, 100~500 weight part inorganic salt tougheners, 10~50 weight part high molecular weight water soluble polymers, stirred fast 10~60 minutes;
(3) obtain Lignins shield grouting additive liquid product after the cooling, spraying drying obtains the pressed powder product;
(4) described linking agent is one or more mixtures in formaldehyde, trimeric cyanamide, polyvalent alcohol, the polyamine; Air entrapment agent is one or more mixtures in rosin soap, colophonium pyrolytic polymer, anion surfactant and the multiple element compound thereof.
Described inorganic salt toughener is the general inorganic salt toughener in this area, and optimal selection is one or more mixtures in sodium sulfate, nitrocalcite, calcium formiate, lime acetate, Tai-Ace S 150, the iron nitrate.
Described high molecular weight water soluble polymer can be the general high molecular weight water soluble polymer in this area, and optimal selection is one or more mixtures in polyoxyethylene glycol, carboxymethyl cellulose, Natvosol, polyacrylate, the polyacrylamide.
During use, grouting additive of the present invention can dry powder or aqueous solution form be added in the metro shield grouting, its volume is 0.3%~0.6% of a cement weight, optimum volume is 0.4%~0.5%.
The present invention's advantageous effect compared with prior art:
1. the present invention is in conjunction with chemical reaction and physics preparation method.Both improved the molecular weight of sulfonated lignin, improved stabilization, reached the many-sided requirement of slip casting in conjunction with preparation method flexibly again mortar from molecular structure.
2. product of the present invention is compared with existing admixture, has utilized papermaking wastewater, plays the effect of protection environment; Main raw material derives from renewable resources simultaneously, reduces the consumption of ore resource, has also reduced the raw materials cost of metro shield grouting additive.
3. this admixture has good stabilization to shield grouting.Because the molecular weight of sulfonated lignin has increased after the modification, added air entrapment agent and high molecular weight water soluble polymer compound, the stability of injecting paste material is significantly improved.Mortar is not easy the layering of emanating, and is difficult for blocking pipeline during pumping, and it is stronger to the supporting role on stratum to inject the back.
4. product of the present invention has overcome the effect of patent (ZL98116516.8) product to the excessive slow setting of slip casting.After adding product of the present invention, slip casting has suitable time of coagulation, in time provides when guaranteeing the mortar pumpability to the fixing of section of jurisdiction with to the supporting role of soil layer.This admixture can also change the rheological of slip casting, reduces pumping resistance, is not easy blocking pipe during pumping.
Embodiment
Embodiment 1
At first get modified lignin mahogany sulfonate concrete high efficiency water reducing agent 1000 grams that adopt patent (ZL98116516.8) technology to produce, be dissolved in the 1500 gram water, warming while stirring to 80 ℃.Add 50 gram formaldehyde, reaction 2h.Add 5 gram colophonium pyrolytic polymers, 100 gram nitrocalcite, 50 gram sodium sulfate, 20 parts of carboxymethyl celluloses (degree of crosslinking is 1000), stirred 30 minutes.Obtain the metro shield grouting additive liquid product after the cooling, the spray-dried again solid dry powder that makes.
Embodiment 2
At first get modified lignin mahogany sulfonate concrete high efficiency water reducing agent 1000 grams that adopt patent (ZL98116516.8) technology to produce, be dissolved in the 1500 gram water, warming while stirring to 90 ℃.Add 50 gram trimeric cyanamides, reaction 1.5h.Add 5 gram dodecyl sulfates, 200 gram calcium formiates, 25 parts of carboxymethyl celluloses (degree of crosslinking is 800), stirred 30 minutes.Obtain the metro shield grouting additive liquid product after the cooling, the spray-dried again solid dry powder that makes.
Embodiment 3
At first get modified lignin mahogany sulfonate concrete high efficiency water reducing agent 1000 grams that adopt patent (ZL98116516.8) technology to produce, be dissolved in the 1000 gram water, warming while stirring to 80 ℃.Add 50 gram ethylene glycol, reaction 2h.Add 20 gram rosin soaps, 200 gram lime acetates, 10 parts of sodium polyacrylates (molecular weight is 1,000,000), stirred 20 minutes.Obtain the metro shield grouting additive liquid product after the cooling, the spray-dried again solid dry powder that makes.
Embodiment 4
At first get modified lignin mahogany sulfonate concrete high efficiency water reducing agent 1000 grams that adopt patent (ZL98116516.8) technology to produce, be dissolved in the 1500 gram water, warming while stirring to 90 ℃.Add 80 gram quadrols, reaction 1h.Add 5 gram colophonium pyrolytic polymers, 200 gram iron nitrates, 100 gram Tai-Ace S 150,30 parts of Natvosols (degree of crosslinking is 1000), stirred 30 minutes.Obtain the metro shield grouting additive liquid product after the cooling, the spray-dried again solid dry powder that makes.
Embodiment 5
At first get modified lignin mahogany sulfonate concrete high efficiency water reducing agent 1000 grams that adopt patent (ZL98116516.8) technology to produce, be dissolved in the 1500 gram water, warming while stirring to 60 ℃.Add 80 gram formaldehyde, reaction 4h.Add 5 gram fat alcohol polyethylene ether sodium sulfate, 200 gram Tai-Ace S 150,10 parts of polyacrylamides (molecular weight is 1,000 ten thousand), stirred 30 minutes.Obtain the metro shield grouting additive liquid product after the cooling, the spray-dried again solid dry powder that makes.
Below be the effect explanation of the admixture produced of the embodiment of the invention, wherein table 1 is an admixture of the present invention and the influence of the different volumes of naphthalene series additive to the injecting paste material bleeding rate; The different volumes of table 2 admixture of the present invention and naphthalene series additive are to the injecting paste material influence of time of coagulation; Table 3 admixture of the present invention and the different volumes of naphthalene series additive are the influences to injecting paste material ultimate compression strength; Data presentation, admixture of the present invention are added to the effect that obtains in the metro shield grouting and obviously are better than existing admixture.
Table 1
Table 2
Table 3

Claims (4)

1. the preparation method of a Lignins metro shield grouting additive is characterized in that may further comprise the steps:
(1) gets 1000 weight part modified lignin mahogany sulfonate concrete high efficiency water reducing agents, be dissolved in and be heated to 60~100 ℃ in 1000~2000 weight parts waters while stirring, add 20~200 weight part linking agents, carry out polycondensation 0.5~10h;
(2) add 1~50 weight part air entrapment agent, 100~500 weight part inorganic salt tougheners, 10~50 weight part high molecular weight water soluble polymers, stirred 10~60 minutes;
(3) obtain liquid product after the cooling, drying obtains the pressed powder product;
Described modified lignin mahogany sulfonate concrete high efficiency water reducing agent prepares according to the ZL98116516.8 patent; Described linking agent is one or more mixtures in formaldehyde, trimeric cyanamide, polyvalent alcohol, the polyamine; Air entrapment agent is one or more mixtures in rosin soap, colophonium pyrolytic polymer, anion surfactant or their the multiple element compound.
2. preparation method according to claim 1 is characterized in that described inorganic salt toughener is one or more mixtures in sodium sulfate, nitrocalcite, calcium formiate, lime acetate, Tai-Ace S 150, the iron nitrate.
3. preparation method according to claim 1 and 2 is characterized in that described high molecular weight water soluble polymer refers to one or more mixtures in polyoxyethylene glycol, carboxymethyl cellulose, Natvosol, polyacrylate, the polyacrylamide.
4. the Lignins metro shield grouting additive of the described method of claim 1 preparation.
CNB2005100326558A 2005-01-04 2005-01-04 Lignins metro shield grouting additive and its preparation method Expired - Fee Related CN100400458C (en)

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Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101357831B (en) * 2008-09-02 2011-01-19 华南理工大学 Melamine modified lignosulphonate high efficiency water reducing agent, preparation method and application thereof
CN102001847B (en) * 2010-10-21 2013-01-16 山东大学 Paste quick-setting grouting material and preparation method thereof
CN102849976B (en) * 2012-10-10 2014-01-22 江苏博特新材料有限公司 Additive capable of improving durability of steam-cured concrete, and concrete coarse aggregate treated thereby
CN105884243A (en) * 2014-09-03 2016-08-24 安徽皖科新科技发展有限公司 Concrete enhancer and preparation and application method thereof
CN105084804B (en) * 2015-07-31 2017-04-12 长沙矿山研究院有限责任公司 Air entraining agent used for reducing entrapped air on surface of filling body and preparation method and application of air entraining agent
CN109180099A (en) * 2018-09-14 2019-01-11 北京城建十六建筑工程有限责任公司 It is a kind of for pouring the concrete material, additive and application method of pier stud

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1997013732A2 (en) * 1995-10-11 1997-04-17 Alcell Technologies Inc. Sulfomethylolated lignin-based concrete admixtures
CN1208027A (en) * 1998-07-21 1999-02-17 华南理工大学 Efficient concrete water reducing agent of modified lignosulphonate and its preparation

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1997013732A2 (en) * 1995-10-11 1997-04-17 Alcell Technologies Inc. Sulfomethylolated lignin-based concrete admixtures
CN1208027A (en) * 1998-07-21 1999-02-17 华南理工大学 Efficient concrete water reducing agent of modified lignosulphonate and its preparation

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