CN106117482B - A kind of modified high-thin arch dam naphthalene water reducer and preparation method thereof - Google Patents
A kind of modified high-thin arch dam naphthalene water reducer and preparation method thereof Download PDFInfo
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- CN106117482B CN106117482B CN201610497279.8A CN201610497279A CN106117482B CN 106117482 B CN106117482 B CN 106117482B CN 201610497279 A CN201610497279 A CN 201610497279A CN 106117482 B CN106117482 B CN 106117482B
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- 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
- C08G16/00—Condensation polymers of aldehydes or ketones with monomers not provided for in the groups C08G4/00 - C08G14/00
- C08G16/02—Condensation polymers of aldehydes or ketones with monomers not provided for in the groups C08G4/00 - C08G14/00 of aldehydes
- C08G16/04—Chemically modified polycondensates
-
- 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
- C04B24/16—Sulfur-containing compounds
- C04B24/20—Sulfonated aromatic compounds
- C04B24/22—Condensation or polymerisation products thereof
- C04B24/226—Sulfonated naphtalene-formaldehyde condensation products
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- 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
- C08G16/00—Condensation polymers of aldehydes or ketones with monomers not provided for in the groups C08G4/00 - C08G14/00
- C08G16/02—Condensation polymers of aldehydes or ketones with monomers not provided for in the groups C08G4/00 - C08G14/00 of aldehydes
- C08G16/0212—Condensation polymers of aldehydes or ketones with monomers not provided for in the groups C08G4/00 - C08G14/00 of aldehydes with acyclic or carbocyclic organic compounds
- C08G16/0218—Condensation polymers of aldehydes or ketones with monomers not provided for in the groups C08G4/00 - C08G14/00 of aldehydes with acyclic or carbocyclic organic compounds containing atoms other than carbon and hydrogen
- C08G16/0231—Condensation polymers of aldehydes or ketones with monomers not provided for in the groups C08G4/00 - C08G14/00 of aldehydes with acyclic or carbocyclic organic compounds containing atoms other than carbon and hydrogen containing nitrogen
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- 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
-
- 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
- C04B2103/308—Slump-loss preventing agents
Abstract
The present invention relates to a kind of preparation methods of modified high-thin arch dam naphthalene water reducer, belong to concrete admixture field, its preparation method comprises the following steps：(1) a kind of sulfonation hydroxymethylphenol is prepared using phenol, sulfonating agent and formaldehyde；(2) using homologue, sulfonation hydroxymethylphenol, hydroxy amino naphthalene sulfonic acids, the concentrated sulfuric acid, phosphoric acid and formaldehyde of naphthalene etc., modified high-thin arch dam naphthalene water reducer is made in sulfonated, hydrolysis, condensation and neutralization four-stage.The present invention introduces substantial amounts of amino, hydroxyl, phosphate and phenyl ring in the molecular structure of water-reducing agent, while naphthalene water reducer high water reducing rate is kept, it can delay the aquation of cement, then improving the slump-retaining of concrete can, it is allowed to also have higher fluidity after 2h, is readily transported and constructs；Preparation process of the present invention is simple, easy to use, effect is good, highly practical.
Description
Technical field
The invention belongs to the technical field of concrete additives in construction material, and in particular to a kind of modified high-thin arch dam naphthalene system
Water-reducing agent, the preparation method of more particularly to this kind water-reducing agent.
Background technology
With the fast development of China's economy, the constantly improve of foundation construction facility gets over the demand of concrete admixture
Come bigger.Water-reducing agent is a kind of additive with water-reducing effect, can significantly improve the workability and mobility of concrete, is improved
The intensity and durability of concrete；Concrete workability and stream can significantly be improved on the premise of folk prescription water consumption is not increased
Dynamic property；Or it is essentially identical in concrete flowability and under the conditions of not influencing workability, coagulation local prescription water consumption is reduced, reduces water
Glue ratio saves folk prescription gel material content.Water-reducing agent has become the 5th kind in addition to cement, sand, stone, water of modern concrete must
Want component.
As the representative of second generation water-reducing agent, naphthalene water reducer have water-reducing rate is high, cement adaptability is good, performance is stable,
The features such as moderate is current domestic production amount maximum, using one of most wide water-reducing agent.But concrete batching system
Slump Time losing of Large it is fast, bring larger difficulty to pumping, the processes such as pouring or cause concrete vibrating unreal, bee occur
Nest pitted skin, influences component quality.
Many producers inhibit cement aquation early period using the retarder such as a certain amount of sodium gluconate, white sugar are compounded at present
Method reduce fresh concrete slump-loss, but easily occur fresh concrete bleeding early period, later stage in use
The phenomenon that liquidity value added is still very fast also results in early strength of concrete and is affected.Therefore, it is necessary to from naphthalene water reducer
Configuration aspects are started with, and improve the faster performance deficiency of Slump Time losing of Large of naphthalene water reducer, to meet market to product
The requirement of energy.
The content of the invention
Present invention seek to address that the existing faster performance deficiency of naphthalene water reducer Slump Time losing of Large, provides a kind of slump
Degree keeps excellent, water-reducing property is high and does not influence the modification high-thin arch dam naphthalene water reducer of early strength of concrete.
Those skilled in the art have found, in the condensation step of naphthalene water reducer synthesis, introduce amino, hydroxyl, phosphoric acid
The groups such as base and phenyl ring, not only water-reducing property is promoted obtained modification high-thin arch dam naphthalene water reducer, but also with excellent
Slump-retaining energy.
Those skilled in the art also found that after above-mentioned group is introduced, obtained water-reducing agent product only slightly prolongs
Concrete coagulating time has been grown, and has not interfered with the early strength of concrete.
Different from by the simple compounding use such as sodium gluconate or aminosulfonic water-reducing agent, the present invention is directly in the prior art
It is connected in naphthalene water reducer molecular structure and introduces functional groups, there is modified naphthalene water reducer molecule and delay cement water
The effect of change makes diminishing agent molecule only be covered and fail by hydrolysis product of cement soon, can effectively reduce and newly mix coagulation
Native slump-loss keeps its mobility, and avoids defect directly caused by compounding retarder.
A kind of preparation method of modified high-thin arch dam naphthalene water reducer, comprises the following steps：
(1) preparation of sulfonation hydroxymethylphenol：
A certain amount of phenol, sulfonating agent and water are put into a kettle, and 40~50 DEG C are heated in the case where being stirred continuously；It adds in
The pH value that 32% liquid caustic soda adjusts reaction system is 8~9；Formaldehyde is added dropwise, rate of addition should be controlled during dropwise addition, makes system temperature
Degree is no more than 70 DEG C；After being added dropwise, 80~90 DEG C and 4~5h of isothermal reaction are heated to；Stop heating, be cooled to 40 DEG C or so
Discharging is to get sulfonation hydroxymethylphenol.
(2) preparation of modified high-thin arch dam naphthalene water reducer：
(1) sulfonation：The homologue of naphthalene is put into reaction kettle and heating is melted to 130~135 DEG C, adds in 98% concentrated sulfuric acid,
In 150~170 DEG C of 3~4h of sulfonating reaction, sulfonation material is obtained；
(2) hydrolyze：100~130 DEG C are cooled to, adds in a certain amount of phosphoric acid and water, hydrolyzes 1~2h；
(3) it is condensed：Material through hydrolysing step is cooled to 90~105 DEG C, adds in sulfonation hydroxymethylphenol and hydroxy amino
Naphthalene sulfonic acids adds formaldehyde, and 3~4h of condensation reaction is carried out at 100~105 DEG C；
(4) neutralize：Aforementioned condensation material, which is transferred to, to be neutralized kettle and adds in 32% liquid caustic soda and water, and reactant is neutralized to pH value for 8
~10 to get to the modified high-thin arch dam naphthalene water reducer.
Sulfonating agent in the sulfonation hydroxymethylphenol preparation process is sodium sulfite, sodium hydrogensulfite or sodium pyrosulfite
One or more of mixture.
Formaldehyde in the sulfonation hydroxymethylphenol preparation process:Phenol:The molar ratio of sulfonating agent is (2.0~2.4):1:
(0.5~1.3).
The homologue of the naphthalene is the mixture of one or more of crude naphthalene, methyl naphthalene and betanaphthol.
The hydroxy amino naphthalene sulfonic acids is 1- amino -2- hydroxyl -4- naphthalene sulfonic acids, 4- amino -3- hydroxyls -1-naphthalene sulfonic aicd, 5-
The mixture of one or more of Amide-6-hydroxy-2-naphthalene sulfonic acids, 6- amino-4-hydroxy-2-naphthalonesulfonic acids, dosage are naphthalene
The 2~6% of homologue gross mass.
The concentrated sulfuric acid:The molar ratio of the homologue of naphthalene is (1.1~1.8):1, the phosphoric acid dosage is concentrated sulfuric acid quality
4~12%.
The sulfonation hydroxymethylphenol dosage is the 5~14% of the homologue gross mass of naphthalene, the formaldehyde:The homologue of naphthalene
Molar ratio be (0.8~1.4):1.
Compared with prior art, the present invention has following features and advantageous effect：
The present invention introduces substantial amounts of amino, hydroxyl and phosphate and phenyl ring in the molecular structure of water-reducing agent, is keeping naphthalene
While based water reducer high water reducing rate, the aquation of cement can be delayed, then improve the slump-retaining energy of concrete, be allowed to
There is higher fluidity after 2h, be readily transported and construct.
Preparation process of the present invention is simple, easy to use, effect is good, highly practical.
Specific embodiment
Below with specific embodiment come the embodiment that the present invention will be described in detail, whereby to the present invention how application technology hand
Section solves technical problem, and the realization process for reaching technique effect can fully understand and implement according to this.
Embodiment 1：
(1) preparation of sulfonation hydroxymethylphenol：
163.8 parts of phenol, 208.8 parts of sodium hydrogensulfites and 266 parts of water are put into a kettle, are heated to 40 while stirring
~50 DEG C；It adds in 56.4 part of 32% liquid caustic soda and adjusts the pH value of reaction system as 8~9；Temperature control is added dropwise 305 parts of formaldehyde, is added dropwise
Cheng Zhongying controls rate of addition, and system temperature is made to be no more than 70 DEG C；Be heated to after being added dropwise 80~90 DEG C and isothermal reaction 4~
5h；Stop heating, be cooled to 40 DEG C or so dischargings to get sulfonation hydroxymethylphenol A.
(2) a kind of modified high-thin arch dam naphthalene water reducer, preparation process are as follows：
(1) sulfonation：138 parts of crude naphthalenes are put into reaction kettle and 28 parts of methyl naphtho- heating are melted to 130~135 DEG C, are added
Enter 145 part of 98% concentrated sulfuric acid, in 160 DEG C of 3~4h of sulfonating reaction；
(2) hydrolyze：120 DEG C are cooled to, adds in 9.7 parts of phosphoric acid and 100 parts of water, hydrolyzes 1~2h；
(3) it is condensed：95 DEG C are cooled to, adds in 10.8 parts of sulfonation hydroxymethylphenol A and 4.2 parts of 1- amino -2- hydroxyl -4- naphthalenes
Then sulfonic acid adds in 95 parts of formaldehyde, condensation reaction 3h~4h is carried out at 100~105 DEG C；
(4) neutralize：Aforementioned condensation material, which is transferred to, to be neutralized kettle and adds in 148 part of 32% liquid caustic soda and 236 parts of water, and reactant is neutralized
To pH value for 8~10 to get to modified high-thin arch dam naphthalene water reducer.
Embodiment 2：
(1) preparation of sulfonation hydroxymethylphenol：
160.8 parts of phenol, 226.7 sodium sulfites and 299 parts of water are put into a kettle, are heated to 40~50 while stirring
℃；Temperature control is added dropwise 313.5 parts of formaldehyde, and rate of addition should be controlled during dropwise addition, and system temperature is made to be no more than 70 DEG C；It drips
80~90 DEG C and 4~5h of isothermal reaction are heated to after finishing；Stop heating, be cooled to 40 DEG C or so dischargings to get sulfonation methylol
Phenol B.
(2) a kind of modified high-thin arch dam naphthalene water reducer, preparation process are as follows：
(1) sulfonation：138 parts of crude naphthalenes are put into reaction kettle and 28 parts of methyl naphtho- heating are melted to 130~135 DEG C, are added
Enter 145 part of 98% concentrated sulfuric acid, in 160 DEG C of 3~4h of sulfonating reaction；
(2) hydrolyze：120 DEG C are cooled to, adds in 9.7 parts of phosphoric acid and 100 parts of water, hydrolyzes 1~2h；
(3) it is condensed：95 DEG C are cooled to, adds in 19.9 parts of sulfonation hydroxymethylphenol B and 5.8 parts of 4- amino -3- hydroxyl -1- naphthalenes
Then sulfonic acid adds in 95 parts of formaldehyde, condensation reaction 3h~4h is carried out at 100~105 DEG C；
(4) neutralize：Aforementioned condensation material, which is transferred to, to be neutralized kettle and adds in 148 part of 32% liquid caustic soda and 239 parts of water, and reactant is neutralized
To pH value for 8~10 to get to modified high-thin arch dam naphthalene water reducer.
Embodiment 3：
(1) preparation of sulfonation hydroxymethylphenol：
With the preparation method of sulfonation hydroxymethylphenol in embodiment 1.
(2) a kind of modified high-thin arch dam naphthalene water reducer, preparation process are as follows：
(1) sulfonation：162 parts of industrial naphtho- heating are put into reaction kettle and are melted to 130~135 DEG C, add in 163.7 part 98%
The concentrated sulfuric acid, in 160 DEG C of 3~4h of sulfonating reaction；
(2) hydrolyze：120 DEG C are cooled to, adds in 8.2 parts of phosphoric acid and 100 parts of water, hydrolyzes 1~2h；
(3) it is condensed：95 DEG C are cooled to, adds in 10.5 parts of sulfonation hydroxymethylphenol A and 5.7 parts of 1- amino -2- hydroxyl -4- naphthalenes
Then sulfonic acid adds in 118 parts of formaldehyde, 3~4h of condensation reaction is carried out at 100~105 DEG C；
(4) neutralize：Aforementioned condensation material, which is transferred to, to be neutralized kettle and adds in 162 part of 32% liquid caustic soda and 245 parts of water, and reactant is neutralized
To pH value for 8~10 to get to modified high-thin arch dam naphthalene water reducer.
Embodiment 4：
(1) preparation of sulfonation hydroxymethylphenol：
157 parts of phenol, 208.3 parts of sodium hydrogensulfites and 254 parts of water are put into a kettle, it is heated to 40 while stirring~
50℃；It adds in 60.7 part of 32% liquid caustic soda and adjusts the pH value of reaction system as 8~9；Temperature control is added dropwise 320 parts of formaldehyde, and process is added dropwise
In should control rate of addition, make system temperature be no more than 70 DEG C；Be heated to after being added dropwise 80~90 DEG C and isothermal reaction 4~
5h；Stop heating, be cooled to 40 DEG C or so dischargings to get sulfonation hydroxymethylphenol C.
(2) a kind of modified high-thin arch dam naphthalene water reducer, preparation process are as follows：
(1) sulfonation：116 parts of crude naphthalenes are put into reaction kettle and 52 parts of methyl naphtho- heating are melted to 130~135 DEG C, are added
Enter 174.5 part of 98% concentrated sulfuric acid, in 160 DEG C of 3~4h of sulfonating reaction；
(2) hydrolyze：120 DEG C are cooled to, adds in 7.5 parts of phosphoric acid and 100 parts of water, hydrolyzes 1~2h；
(3) it is condensed：95 DEG C are cooled to, adds in 22.7 parts of sulfonation hydroxymethylphenol C and 9.2 parts of 4- amino -3- hydroxyl -1- naphthalenes
Then sulfonic acid adds in 111.3 parts of formaldehyde, 3~4h of condensation reaction is carried out at 100~105 DEG C；
(4) neutralize：Aforementioned condensation material, which is transferred to, to be neutralized kettle and adds in 146 part of 32% liquid caustic soda and 277 parts of water, and reactant is neutralized
To pH value for 8~10 to get to modified high-thin arch dam naphthalene water reducer.
Embodiment 5：
(1) preparation of sulfonation hydroxymethylphenol：
150 parts of phenol, 196.8 parts of sodium pyrosulfites and 214 parts of water are put into a kettle, it is heated to 40 while stirring~
50℃；It adds in 120.5 part of 32% liquid caustic soda and adjusts the pH value of reaction system as 8~9；Temperature control is added dropwise 318.7 parts of formaldehyde, is added dropwise
Cheng Zhongying controls rate of addition, and system temperature is made to be no more than 70 DEG C；Be heated to after being added dropwise 80~90 DEG C and isothermal reaction 4~
5h；Stop heating, be cooled to 40 DEG C or so dischargings to get sulfonation hydroxymethylphenol D.
(2) a kind of modified high-thin arch dam naphthalene water reducer, preparation process are as follows：
(1) sulfonation：120 parts of crude naphthalenes and 55 parts of betanaphthols are put into reaction kettle and are heated and are melted to 130~135 DEG C, are added
Enter 148.7 part of 98% concentrated sulfuric acid, in 160 DEG C of 3~4h of sulfonating reaction；
(2) hydrolyze：120 DEG C are cooled to, adds in 15.2 parts of phosphoric acid and 100 parts of water, hydrolyzes 1~2h；
(3) it is condensed：95 DEG C are cooled to, adds in 15.8 parts of sulfonation hydroxymethylphenol D and 5.3 parts of 5- Amide-6-hydroxy-2s-naphthalenes
Then sulfonic acid adds in 104.5 parts of formaldehyde, 3~4h of condensation reaction is carried out at 100~105 DEG C；
(4) neutralize：Aforementioned condensation material, which is transferred to, to be neutralized kettle and adds in 149 part of 32% liquid caustic soda and 258 parts of water, and reactant is neutralized
To pH value for 8~10 to get to modified high-thin arch dam naphthalene water reducer.
Embodiment 6：
(1) preparation of sulfonation hydroxymethylphenol：
With embodiment 5.
(2) a kind of modified high-thin arch dam naphthalene water reducer, preparation process are as follows：
(1) sulfonation：128 parts of crude naphthalenes and 46 parts of betanaphthols are put into reaction kettle and are heated and are melted to 130~135 DEG C, are added
Enter 150 part of 98% concentrated sulfuric acid, in 160 DEG C of 3~4h of sulfonating reaction；
(2) hydrolyze：120 DEG C are cooled to, adds in 10.4 parts of phosphoric acid and 100 parts of water, hydrolyzes 1~2h；
(3) it is condensed：95 DEG C are cooled to, adds in 17.4 parts of sulfonation hydroxymethylphenol D and 7.0 parts of 6- amino-4-hydroxy -2- naphthalenes
Then sulfonic acid adds in 132 parts of formaldehyde, 3~4h of condensation reaction is carried out at 100~105 DEG C；
(4) neutralize：Aforementioned condensation material, which is transferred to, to be neutralized kettle and adds in 142 part of 32% liquid caustic soda and 250 parts of water, and reactant is neutralized
To pH value for 8~10 to get to modified high-thin arch dam naphthalene water reducer.
Comparative example：
A kind of synthesis of common naphthalene water reducer comprises the following steps：
(1) sulfonation：162 parts of industrial naphtho- heating are put into reaction kettle and are melted to 130~135 DEG C, 170 part 98% of addition is dense
Sulfuric acid, in 160 DEG C of 3~4h of sulfonating reaction；
(2) hydrolyze：120 DEG C are cooled to, adds in 100 parts of water, hydrolyzes 1~2h；
(3) it is condensed：95 DEG C are cooled to, adds in 110 parts of formalins, 3~4h of condensation reaction is carried out at 100 DEG C；
(4) neutralize：Aforementioned condensation material, which is transferred to, to be neutralized kettle and adds in 140 part of 32% liquid caustic soda and 243 parts of water, and reactant is neutralized
To pH value for 8~10 to get to product.
Application Example 1：
In order to evaluate the performance of the modification high-thin arch dam naphthalene water reducer of the present invention, according to GB/T8077-2012《Outside concrete
Add agent homogeneity test method》Different flowing degree of net paste of cement experiments are carried out.In experiment three kinds of cement be respectively reference cement,
42.5 cement of conch PO of Chinese cement Co., Ltd., Factory production and the crane woods PO of Jiangsu He Lin Cement Co., Ltds production
42.5 cement；Water-reducing agent also selects the FDN naphthalene water reducers of Shandong factory to carry out pair in addition to above-described embodiment and comparative example
Than volume is 0.75% (to be counted on the basis of rolling over the weight of solid rear cement), and result of the test is shown in Table 1.
The flowing degree of net paste of cement of the different naphthalene water reducers of table 1
By 1 result of table as it can be seen that pulp flowage of the modification high-thin arch dam naphthalene water reducer of the present invention in three kinds of cement
Degree especially gradual loss is totally better than the common naphthalene water reducer in two kinds of comparative examples.
Application Example 2：
According to GB 8076-2008《Concrete admixture》Changing for the present invention is mixed in the relevant regulations of middle high efficiency water reducing agent, evaluation
Water-reducing rate, air content, setting time and the compression strength of the concrete of property high-thin arch dam naphthalene water reducer.Experiment is using reference water
Mud, modulus of fineness are 2.6 middle sand, and the rubble of 5~20mm continuous gradings, concrete mix is cement:Sand:Stone=330:
768:1152, adjustment water consumption makes fresh concrete initial slump for 80mm ± 10mm, and the volume of water-reducing agent is cement weight
0.75% (folding solid).Result of the test is shown in Table 2.
Table 2 mixes the concrete performance of the present invention
By 2 result of table as it can be seen that water-reducing rate is reachable when the modification high-thin arch dam naphthalene water reducer volume of the present invention is 0.75%
More than 23%, slightly above common naphthalene water reducer；Air content is compared with blank group only to have a small increase, and is non-research work of air entrained type diminishing
Agent；Setting time has compared a degree of extension with common naphthalene water reducer, but for 7d, 28d compression strength without bad shadow
It rings.
Application Example 3：
According to GB 8076-2008《Concrete admixture》The relevant regulations of middle pumping admixture, the evaluation present invention's is modified high
The naphthalene water reducer that collapses is protected to be re-dubbed pumping admixture and mix air content, setting time, the slump and the 1h ongoing change after concrete
Amount and compression strength.Experiment is using reference cement, and modulus of fineness is 2.6 middle sand, the rubble of 5~20mm continuous gradings, coagulation
Native match ratio is cement:Sand:Stone:Water=360:864:1056:185；Pumping admixture volume is 1.2%, is formulated as naphthalene water reducer:
Rosin air entraining agent:Sodium gluconate:Water=0.4:0.03:0.03:0.54, result of the test see the table below 3.
Table 3 mixes the concrete performance after the pumping admixture that the present invention is re-dubbed
By 3 result of table as it can be seen that mixing concrete after being re-dubbed pumping admixture with the modification high-thin arch dam naphthalene water reducer of the present invention,
It is compared with normal concrete, air content and 7d, 28d compression strength are substantially unaffected, and concrete slump and the degree of expansion that collapses, especially
It is that 1h ongoing change amounts are obviously reduced, and is more advantageous to concrete long-distance transportation and pumping construction.
Although the present invention is described by embodiment, embodiment is not used for limiting the present invention.Art technology
Personnel can make various modifications and improvement, such as the adjustment of component ratio or time range in the scope of the spirit of the present invention,
Effect after this adjustment is predictable, so it is equally within protection scope of the present invention.Therefore the protection of the present invention
Scope should be subject to the protection domain that the identical or equivalent technical characteristic of claims hereof is defined.
Claims (6)
1. a kind of preparation method of modified high-thin arch dam naphthalene water reducer, which is characterized in that comprise the following steps：
Step 1: the preparation of sulfonation hydroxymethylphenol：
A certain amount of phenol, sulfonating agent and water are put into a kettle, and 40 ~ 50 DEG C are heated in the case where being stirred continuously；Add in 32% liquid
The pH value that alkali adjusts reaction system is 8 ~ 9；Formaldehyde is added dropwise, rate of addition should be controlled during dropwise addition, system temperature is made not surpass
Cross 70 DEG C；80 ~ 90 DEG C and 4 ~ 5h of isothermal reaction are heated to after being added dropwise；Stop heating, be cooled to 40 DEG C or so discharging to get
Sulfonation hydroxymethylphenol；
Step 2: the preparation of modified high-thin arch dam naphthalene water reducer：
（1）Sulfonation：The homologue of naphthalene is put into reaction kettle and heating is melted to 130 ~ 135 DEG C, adds in 98% concentrated sulfuric acid, 150 ~
170 DEG C of 3 ~ 4h of sulfonating reaction, obtain sulfonation material；The homologue of naphthalene is methyl naphthalene；
（2）Hydrolysis：100 ~ 130 DEG C are cooled to, adds in a certain amount of phosphoric acid and water, hydrolyzes 1 ~ 2h；
（3）Condensation：Material through hydrolysing step is cooled to 90 ~ 105 DEG C, adds in sulfonation hydroxymethylphenol and hydroxy amino naphthalene sulphur
Acid adds formaldehyde, and 3 ~ 4h of condensation reaction is carried out at 100 ~ 105 DEG C；
（4）It neutralizes：Aforementioned condensation material, which is transferred to, to be neutralized kettle and adds in 32% liquid caustic soda and water, and it is 8 ~ 10 that reactant is neutralized to pH value, i.e.,
Obtain the modified high-thin arch dam naphthalene water reducer.
2. the preparation method of modified high-thin arch dam naphthalene water reducer according to claim 1, it is characterised in that：The sulfonating agent
For the mixture of one or more of sodium sulfite, sodium hydrogensulfite or sodium pyrosulfite.
3. the preparation method of modified high-thin arch dam naphthalene water reducer according to claim 1, it is characterised in that：The formaldehyde:
Phenol:The molar ratio of sulfonating agent is (2.0 ~ 2.4):1 : (0.5~1.3).
4. the preparation method of modified high-thin arch dam naphthalene water reducer according to claim 1, it is characterised in that：The amino hydroxyl
Base naphthalene sulfonic acids is 1- amino -2- hydroxyl -4- naphthalene sulfonic acids, 4- amino -3- hydroxyls -1-naphthalene sulfonic aicd, 5- Amide-6-hydroxy-2s-naphthalene sulphur
The mixture of one or more of acid, 6- amino-4-hydroxy-2-naphthalonesulfonic acids, dosage are the 2 ~ 6% of the homologue gross mass of naphthalene.
5. the preparation method of modified high-thin arch dam naphthalene water reducer according to claim 1, it is characterised in that：The dense sulphur
Acid:The molar ratio of the homologue of naphthalene is (1.1 ~ 1.8):1, the phosphoric acid dosage is the 4 ~ 12% of concentrated sulfuric acid quality.
6. the preparation method of modified high-thin arch dam naphthalene water reducer according to claim 1, it is characterised in that：The sulfonation hydroxyl
Methylphenol dosage is the 5 ~ 14% of the homologue gross mass of naphthalene, the formaldehyde:The molar ratio of the homologue of naphthalene is (0.8 ~ 1.4):
1。
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| CN109293885B (en) * | 2018-09-28 | 2021-04-20 | 镇江苏博特新材料有限公司 | Phosphate group-containing water reducing agent and preparation method thereof |
| CN113121771B (en) * | 2019-12-30 | 2022-12-02 | 江苏苏博特新材料股份有限公司 | Air-entraining modified naphthalene water reducer and preparation method thereof |
| CN112125564B (en) * | 2020-06-15 | 2022-10-04 | 安徽鑫固环保股份有限公司 | Naphthalene water reducer |
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| CN114105514A (en) * | 2021-12-24 | 2022-03-01 | 莱芜市兆信新材料股份有限公司 | Preparation method of naphthalene water reducer for middle east high-heat area |
| CN115925361A (en) * | 2022-12-16 | 2023-04-07 | 浙江桐化建材股份有限公司 | Dry-mixed plastering mortar and preparation method thereof |
| CN116731275B (en) * | 2023-07-06 | 2024-01-26 | 湖北腾辰科技股份有限公司 | Mud-resistant modified naphthalene water reducer and preparation method thereof |
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