CN108299650A - A kind of grouting agent polycarboxylate water-reducer and preparation method thereof - Google Patents
A kind of grouting agent polycarboxylate water-reducer and preparation method thereof Download PDFInfo
- Publication number
- CN108299650A CN108299650A CN201711434212.0A CN201711434212A CN108299650A CN 108299650 A CN108299650 A CN 108299650A CN 201711434212 A CN201711434212 A CN 201711434212A CN 108299650 A CN108299650 A CN 108299650A
- Authority
- CN
- China
- Prior art keywords
- polycarboxylate water
- grouting agent
- preparation
- reducer
- maleic anhydride
- 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.)
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
- C08G81/02—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers at least one of the polymers being obtained by reactions involving only carbon-to-carbon unsaturated bonds
- C08G81/024—Block or graft polymers containing sequences of polymers of C08C or C08F and of polymers of C08G
- C08G81/025—Block or graft polymers containing sequences of polymers of C08C or C08F and of polymers of C08G containing polyether sequences
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/24—Macromolecular compounds
- C04B24/28—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B40/00—Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
- C04B40/0028—Aspects relating to the mixing step of the mortar preparation
- C04B40/0039—Premixtures of ingredients
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/30—Water reducers, plasticisers, air-entrainers, flow improvers
- C04B2103/302—Water reducers
Abstract
The invention discloses a kind of grouting agent polycarboxylate water-reducers and preparation method thereof, maleic anhydride of styrene copolymer resins are mixed with methoxy poly (ethylene glycol) ether, butanol atactic polyether, p-methyl benzenesulfonic acid, 6~18 hours obtained polycarboxylate water-reducers of heating reaction in nitrogen atmosphere, reaction temperature are 140~180 DEG C；Wherein, the molecular weight of the maleic anhydride of styrene copolymer resins is 4000~6000；The molar ratio of copolymer resins monomer styrene and maleic anhydride is 1: 1；The molecular weight of the methoxy poly (ethylene glycol) ether is 400~3000；The molecular weight of the butanol atactic polyether is 1000~2500.The pure grouting agent polycarboxylate water-reducer of one-step synthesis of the present invention, it is preferable with the compatibility of various cement, and the initial flow degree for preparing grouting agent is both less than 17s.
Description
Technical field
The present invention relates to a kind of cement additives, and in particular to a kind of grouting agent polycarboxylate water-reducer and its preparation side
Method.
Background technology
With the fast development of national basis facility, the completion time of project can be greatly shortened using concrete pre-member, for just
In the transport of concrete pre-member, many pre-members are all hollow structures, after only arriving in-site installation in place, just to its hole
It is filled.
Grouting material is used for the filling of the girder pre-stressed pipeline of post-tensioning, to prevent the burn into of prestressing steel from ensureing prestressing tendon
The effective stress transfer between concrete structure.Mud-jacking technology should make slurry in duct full closely knit, and slurry keeps certain
PH value range, fully wrapped around prestressing steel, slurry hardening after have higher intensity and elasticity modulus and expansion shrinkage-void
And bonding force.In general, grouting agent is constituted by high efficiency water reducing agent, micro-expanding agent, mineral admixture, in use, grouting agent is dissolved in
In water, cement is added, stirs evenly to form grouting material slurries.
According to the relevant regulations in JTG/T F50-2011 highway bridge and culvert construction technique normalizings, in low water-cement ratio handle
The indices of post-tensioning hole path pressure grouting slurries all do qualification, are very difficult, this is also to cause new standard grouting agent price big
The reason of amplitude goes up.The ratio of mud that new bridge gauge defines grouting material is 0.26~0.28, and it is 10 to make consistency on this basis
~17 seconds mud jacking liquid.（Referring to JTG/T F50-2011 highway bridge and culvert construction technique normalizing table 7.9.3 post-tensioned prestressings duct
Mud jacking size performance index）
Due to needing to reach low water-cement ratio, the water-reducing property of grouting agent is required to improve, experiment finds that many water-reducing agents are all difficult to
Reach requirement.In the prior art, the other methods of generally use improve water-reducing rate, for example, Chinese invention patent CN103833260A
A kind of environment-friendly high-efficiency grouting agent is disclosed, is made after mixing using the raw material of following quality：Dodecyl sodium sulfate 1.6 ~
2.4g, 0.2 ~ 1.0g of methylcellulose, 14 ~ 22g of poly carboxylic acid series water reducer, 134 ~ 142g of UEA swelling agents, ultra tiny calcium powder dirt
80 ~ 100g, 36 ~ 64g of gas ash.The ultra tiny calcium powder dirt wherein added, since its grain size is close with SILICA FUME, aged processing
There is fabulous filling and " ball lubrication " effect afterwards, physics water-reducing effect is notable, and water-reducing rate is up to 9% or more.But the party
The ultra tiny calcium dust size requirement used in case is close with SILICA FUME, and different from silicon powder, the fineness of SILICA FUME is small, average grain
Diameter is at 0.1~0.3 micron, it is clear that conventional ultrafine calcium carbonate cannot be satisfied the requirement of the program.This necessarily leads to the program
Cost increases.
In the prior art, the addition for focusing on the research of grouting agent other materials, is specially adapted for pressing without studying
Starch the water-reducing agent of agent, it is therefore necessary to new water-reducing agent be provided, the preparation of grouting agent is used for, it is made to meet the requirement of new bridge gauge.
Invention content
The goal of the invention of the present invention is to provide a kind of grouting agent polycarboxylate water-reducer, meets when grouting agent uses to water ash
Than the requirement with consistency；Another goal of the invention of the present invention is to provide the preparation method of polycarboxylate water-reducer.
To achieve the above object of the invention, the technical solution adopted by the present invention is：A kind of grouting agent polycarboxylate water-reducer
Preparation method, by styrene-maleic anhydride copolymer resin and methoxy poly (ethylene glycol) ether（MPEG）, butanol atactic polyether（BPE）、
P-methyl benzenesulfonic acid mixes, and reaction is heated in nitrogen atmosphere and is made within 6~18 hours, reaction temperature is 140~180 DEG C；
Wherein, the molecular weight of the styrene-maleic anhydride copolymer resin is 4000~6000；Copolymer resins monomer styrene with
The molar ratio of maleic anhydride is 1: 1；The molecular weight of the methoxy poly (ethylene glycol) ether is 400~3000；The butanol randomly gathers
The molecular weight of ether is 1000~2500.
Further technical solution after the completion of reaction, cools to 78~82 DEG C, and the polycarboxylate water-reducer of acquisition and silicon is micro-
Ash is uniformly mixed, and is made powder, and the mass ratio of polycarboxylate water-reducer and the micro- ash of silicon is 1: 4.Since powder, Ke Yifang is made
Just it is used in powdery grouting agent.
In above-mentioned technical proposal, the molal quantity and methoxy of contained acid anhydride unit in the styrene-maleic anhydride copolymer resin
The ratio of base polyglycol ether and the total hydroxyl moles of butanol atactic polyether is more than 2.Methoxy poly (ethylene glycol) ether and butanol without
The mass ratio for advising polyethers is 5~10: 1, and the quality of p-methyl benzenesulfonic acid accounts for 0.5~the 2 ‰ of the quality of total material.
In above-mentioned technical proposal, the styrene-maleic anhydride copolymer resin is the powdery that fineness is less than or equal to 100 mesh
Object.
The molecular weight of preferred technical solution, the methoxy poly (ethylene glycol) ether is 750~3000.Reaction temperature is 160
~180 DEG C.Reaction time is 6~15 hours.
The present invention discloses the grouting agent polycarboxylate water-reducers obtained using above-mentioned preparation method.Wherein, poly- carboxylic
The weight average molecular weight of acid molecule is 10000~30000.
Since above-mentioned technical proposal is used, the present invention has following advantages compared with prior art：
1, the pure grouting agent polycarboxylate water-reducer of one-step synthesis of the present invention（Approximation 100%）, with the compatibilities of various cement compared with
It is good, and the initial flow degree for preparing grouting agent is both less than 17s.
2, in view of it is energy saving and take conveniently, the present invention may be used silicon it is micro- ash be carrier, be made into powder.
3, due to selecting " comb spine " of this raw material of styrene-maleic anhydride copolymer resin as polycarboxylate water-reducer；
" broach " length can be adjusted by the size of adjusting MPEG and BPE molecular weight；It can be by adjusting MPEG and BPE and resin
Relative scale, adjust " broach " density.By the dosage of adjusting BPE, the air content of polycarboxylate water-reducer can be adjusted, to
Regulate and control the intensity of slurry.
4, since harmful substance, thus the grouting agent obtained are not used, do not generated in this product preparation process
It is a kind of product of environment-friendly type with polycarboxylate water-reducer.
Specific implementation mode
With reference to embodiment, the invention will be further described：
Embodiment one：
350 grams of MPEG-800 and 70 gram of BPE-2500 are added in clean flask, start stirring, it is 120 that 210 grams of fineness, which are added,
Purpose styrene-maleic anhydride copolymer toner（Molecular weight 4100）, 1 gram of p-methyl benzenesulfonic acid is added, nitrogen protection is passed through,
Heat to 160-170 DEG C of insulation reaction 9 hours, with the progress of reaction, material becomes transparency liquid gradually from unclear.Instead
It should finish, material is cooled to 80 DEG C with the micro- ash of silicon by 1：4 mass ratio is uniformly mixed and powdery is made.
Embodiment two：
430 grams of MPEG-1500 and 50 gram of BPE-1500 are added in clean flask, start stirring, 150 grams of fineness, which are added, is
The styrene-maleic anhydride copolymer toner of 160 mesh（Molecular weight 4500）, 0.8 gram of p-methyl benzenesulfonic acid is added, nitrogen is passed through
Protection, heats to 170-175 DEG C of insulation reaction 8 hours, and with the progress of reaction, material becomes transparent liquid gradually from unclear
Body.Reaction finishes, and material is cooled to 80 DEG C with the micro- ash of silicon by 1：4 mass ratio is uniformly mixed and powdery is made.
Embodiment three：
455 grams of MPEG-2500 and 55 gram of BPE-1000 are added in clean flask, start stirring, 120 grams of fineness, which are added, is
The styrene-maleic anhydride copolymer toner of 200 mesh（Molecular weight 5500）, 0.5 gram of p-methyl benzenesulfonic acid is added, nitrogen is passed through
Protection, heats to 175-180 DEG C of insulation reaction 7 hours, and with the progress of reaction, material becomes transparent liquid gradually from unclear
Body.Reaction finishes, and material is cooled to 80 DEG C with the micro- ash of silicon by 1：4 mass ratio is uniformly mixed and powdery is made.
By the grouting agent polycarboxylate water-reducer obtained by embodiment one to three according to standard：Highway bridge and culvert construction technology is advised
Model (JTG/T F50-2011) carries out performance detection.
The water-reducing agent of the various embodiments described above is applied in grouting material.
Used raw material in grouting material：
1）Cement：P.O.42.5 Portland cements.
2）Flyash：I grades of ashes, screen over-size≤10%, loss on ignition≤4%.
3）Water-reducing agent：Water-reducing agent prepared by embodiment one to three.
4）Water：Tap water should meet the regulation of JGJ 63.
Experimental comparison's method is as shown in table 1（Each data are mass parts dosage in table 1）.
Table 1
| Number | Cement | Flyash | Water | Water-reducing agent |
| Reference examples | 2700 | 300 | 780 | —— |
| Embodiment one | 2700 | 300 | 780 | 10 |
| Embodiment two | 2700 | 300 | 780 | 10 |
| Embodiment three | 2700 | 300 | 780 | 10 |
Stirring means：The rotating speed of blender should be not less than 1000r/min, and the shape of stirring blade should be with rotational speed matches, leaf
The linear velocity of piece is not preferably less than 10m/s, and maximum linear velocity is preferably limited within 20m/s, and should be able to be met before the deadline
The requirement stirred evenly.
Initial flow degree is listed in table 2 when each embodiment water-cement ratio is 0.26：
Table 2
| Reference examples | Embodiment one | Embodiment two | Embodiment three | |
| Initial flow degree, s | It does not flow | 13.4 | 15.2 | 14.7 |
As can be seen from the table, using styrene-maleic anhydride copolymer resin and methoxy poly (ethylene glycol) ether (MPEG) and butanol
Atactic polyether (BPE) step high temperature esterification synthesizes grouting agent polycarboxylate water-reducer, and grouting agent initial flow is prepared with its powder
Degree is both less than 17s.
Claims (10)
1. a kind of preparation method of grouting agent polycarboxylate water-reducer, it is characterised in that：By styrene-maleic anhydride copolymer resin
It is mixed with methoxy poly (ethylene glycol) ether, butanol atactic polyether, p-methyl benzenesulfonic acid, heating reaction 6~18 hours in nitrogen atmosphere
It is made, reaction temperature is 140~180 DEG C；
Wherein, the molecular weight of the styrene-maleic anhydride copolymer resin is 4000~6000；Copolymer resins monomer styrene with
The molar ratio of maleic anhydride is 1: 1；The molecular weight of the methoxy poly (ethylene glycol) ether is 400~3000；The butanol randomly gathers
The molecular weight of ether is 1000~2500.
2. the preparation method of grouting agent polycarboxylate water-reducer according to claim 1, it is characterised in that：After the completion of reaction,
Cool to 78~82 DEG C, the polycarboxylate water-reducer of acquisition be uniformly mixed with the micro- ash of silicon, be made powder, polycarboxylate water-reducer with
The mass ratio of the micro- ash of silicon is 1: 4.
3. the preparation method of grouting agent polycarboxylate water-reducer according to claim 1, it is characterised in that：The styrene-
The molal quantity of the contained acid anhydride unit hydroxyl total with methoxy poly (ethylene glycol) ether and butanol atactic polyether in maleic anhydride resin
The ratio of molal quantity is more than 2.
4. the preparation method of grouting agent polycarboxylate water-reducer according to claim 1, it is characterised in that：The poly- second of methoxyl group two
The mass ratio of alcohol ether and butanol atactic polyether is 5~10: 1, and the quality of p-methyl benzenesulfonic acid accounts for 0.5~the 2 ‰ of the quality of total material.
5. the preparation method of grouting agent polycarboxylate water-reducer according to claim 1, it is characterised in that：The styrene-
Maleic anhydride resin is the powder that fineness is less than or equal to 100 mesh.
6. the preparation method of grouting agent polycarboxylate water-reducer according to claim 1, it is characterised in that：The methoxyl group is poly-
The molecular weight of glycol ether is 750~3000.
7. the preparation method of grouting agent polycarboxylate water-reducer according to claim 1, it is characterised in that：Reaction temperature is
160~180 DEG C.
8. the preparation method of grouting agent polycarboxylate water-reducer according to claim 1, it is characterised in that：Reaction time is 6
~15 hours.
9. the grouting agent polycarboxylate water-reducer obtained using any preparation method in claim 1-8.
10. grouting agent polycarboxylate water-reducer according to claim 9, it is characterised in that：Polycarboxylic acids molecule is divided equally again
Son amount is 10000~30000.
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| CN201711434212.0A CN108299650A (en) | 2017-12-26 | 2017-12-26 | A kind of grouting agent polycarboxylate water-reducer and preparation method thereof |
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|---|---|---|---|---|
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2017
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Application publication date: 20180720 |