CN106117482A - 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 PDF

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CN106117482A
CN106117482A CN201610497279.8A CN201610497279A CN106117482A CN 106117482 A CN106117482 A CN 106117482A CN 201610497279 A CN201610497279 A CN 201610497279A CN 106117482 A CN106117482 A CN 106117482A
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naphthalene
water reducer
preparation
modified high
arch dam
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CN106117482B (en
Inventor
陈国新
祝烨然
王冬
唐修生
温金保
杜志芹
刘兴荣
蔡明�
付丹华
黄国泓
孙国荣
孙清玉
方绪顺
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Jiangsu Kexing Project Management Co. Ltd.
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NANJING R&D HIGH TECHNOLOGY Co
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G16/00Condensation polymers of aldehydes or ketones with monomers not provided for in the groups C08G4/00 - C08G14/00
    • C08G16/02Condensation polymers of aldehydes or ketones with monomers not provided for in the groups C08G4/00 - C08G14/00 of aldehydes
    • C08G16/04Chemically modified polycondensates
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B24/00Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
    • C04B24/16Sulfur-containing compounds
    • C04B24/20Sulfonated aromatic compounds
    • C04B24/22Condensation or polymerisation products thereof
    • C04B24/226Sulfonated naphtalene-formaldehyde condensation products
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G16/00Condensation polymers of aldehydes or ketones with monomers not provided for in the groups C08G4/00 - C08G14/00
    • C08G16/02Condensation polymers of aldehydes or ketones with monomers not provided for in the groups C08G4/00 - C08G14/00 of aldehydes
    • C08G16/0212Condensation 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
    • C08G16/0218Condensation 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
    • C08G16/0231Condensation 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
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2103/00Function or property of ingredients for mortars, concrete or artificial stone
    • C04B2103/30Water reducers, plasticisers, air-entrainers, flow improvers
    • C04B2103/302Water reducers
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2103/00Function or property of ingredients for mortars, concrete or artificial stone
    • C04B2103/30Water reducers, plasticisers, air-entrainers, flow improvers
    • C04B2103/308Slump-loss preventing agents

Abstract

The present invention relates to the preparation method of a kind of modified high-thin arch dam naphthalene water reducer, belong to concrete admixture field, its preparation method comprises the following steps: (1) uses phenol, sulfonating agent and a kind of sulfonation hydroxymethylphenol of formaldehyde preparation;(2) homologue of naphthalene, sulfonation hydroxymethylphenol, hydroxy amino LOMAR PWA EINECS 246-676-2, concentrated sulphuric acid, phosphoric acid and formaldehyde etc. are used, sulfonated, hydrolyze, be condensed and neutralize four-stage and prepare modified high-thin arch dam naphthalene water reducer.The present invention introduces substantial amounts of amino, hydroxyl, phosphate and phenyl ring in the molecular structure of water reducer, while keeping naphthalene water reducer high water reducing rate, the aquation of cement can be delayed, then the slump-retaining energy of concrete is improved, it is allowed to after 2h also have higher fluidity, it is simple to transport and construct;Preparation technology of the present invention is simple, easy to use, effective, practical.

Description

A kind of modified high-thin arch dam naphthalene water reducer and preparation method thereof
Technical field
The invention belongs to the technical field of concrete additives in construction material, be specifically related to a kind of modified high-thin arch dam naphthalene system Water reducer, particularly to the preparation method of this kind of water reducer.
Background technology
Along with the fast development of China's economy, foundation construction facility the most perfect, to the demand of concrete admixture more Come the biggest.Water reducer is a kind of additive with water-reducing effect, can significantly improve workability and the mobility of concrete, improves The intensity of concrete and durability;Concrete workability and stream can be improved significantly on the premise of not increasing folk prescription water consumption Dynamic property;Or essentially identical in concrete flowability and under the conditions of not affecting workability, reduce concrete folk prescription water consumption, reduce water Glue ratio, saves folk prescription gel material content.Water reducer has become the 5th kind in addition to cement, sand, stone, water of modern concrete must Want component.
As the representative of second filial generation water reducer, naphthalene water reducer has that water-reducing rate is high, cement adaptability is good, stable performance, The features such as moderate cost, are that current domestic production amount is maximum, use one of the widest water reducer.But, its concrete batching system Slump Time losing of Large fast, the process such as pumped, pour brings bigger difficulty, or causes concrete vibrating unreal, honeybee occurs Nest pitted skin, affects component quality.
The most a lot of producers use the retarder such as compounding a certain amount of sodium gluconate, white sugar to suppress cement early stage aquation Method reduce fresh concrete slump-loss, but fresh concrete early stage bleeding, later stage the most easily occur Liquidity value added phenomenon the most faster, also results in early age strength of concrete and is affected.Therefore, it is necessary to from naphthalene water reducer Configuration aspects is started with, and improves the Slump Time losing of Large performance deficiency faster of naphthalene water reducer, to meet market to product The requirement of energy.
Summary of the invention
Present invention seek to address that existing naphthalene water reducer Slump Time losing of Large performance deficiency faster, it is provided that a kind of slump Degree keeps excellent, water-reducing property is high and does not affect the modified high-thin arch dam naphthalene water reducer of early age strength of concrete.
Those skilled in the art find, in the condensation step of naphthalene water reducer synthesis, introduce amino, hydroxyl, phosphoric acid The group such as base and phenyl ring, obtained modified high-thin arch dam naphthalene water reducer not only water-reducing property has promoted, and has had excellence Slump-retaining energy.
Those skilled in the art also finds, after introducing above-mentioned group, obtained water reducer product the most slightly prolongs Grow concrete coagulating time, and do not interfere with the early strength of concrete.
Being different from prior art and use the most compounding to sodium gluconate or aminosulfonic water-reducing agent etc., the present invention is straight It is connected in naphthalene water reducer molecular structure introducing functional groups, makes modified naphthalene water reducer molecule have and delay cement water The effect changed, makes water reducer molecule be covered by hydrolysis product of cement the most too quickly and lose efficacy, it is possible to effectively reduce and newly mix coagulation Soil slump-loss, keep its mobility, and avoid the defect that directly compounding retarder is brought.
The preparation method of a kind of modified high-thin arch dam naphthalene water reducer, comprises the following steps:
(1) preparation of sulfonation hydroxymethylphenol:
Put into a certain amount of phenol, sulfonating agent and water in a kettle., under being stirred continuously, be heated to 40~50 DEG C;Add The pH value of 32% liquid caustic soda regulation reaction system is 8~9;Dropping formaldehyde, should control rate of addition during dropping, make system temperature Degree is less than 70 DEG C;After dropping, it is heated to 80~90 DEG C and isothermal reaction 4~5h;Stop heating, be cooled to about 40 DEG C Discharging, obtains sulfonation hydroxymethylphenol.
(2) preparation of modified high-thin arch dam naphthalene water reducer:
(1) sulfonation: the homologue the heating that put into naphthalene in reactor are melted to 130~135 DEG C, add 98% concentrated sulphuric acid, In 150~170 DEG C of sulfonating reactions 3~4h, obtain sulfonation material;
(2) hydrolysis: be cooled to 100~130 DEG C, adds a certain amount of phosphoric acid and water, hydrolyzes 1~2h;
(3) condensation: be cooled to 90~105 DEG C through the material of hydrolysing step, adds sulfonation hydroxymethylphenol and hydroxy amino LOMAR PWA EINECS 246-676-2, adds formaldehyde, carries out condensation reaction 3~4h at 100~105 DEG C;
(4) neutralize: aforementioned condensation material proceeds to neutralize still and add 32% liquid caustic soda and water, and it is 8 that reactant is neutralized to pH value ~10, i.e. obtain described modified high-thin arch dam naphthalene water reducer.
Sulfonating agent in described sulfonation hydroxymethylphenol preparation process is sodium sulfite, sodium sulfite or sodium pyrosulfite In the mixture of one or more.
Formaldehyde in described sulfonation hydroxymethylphenol preparation process: phenol: the mol ratio of sulfonating agent is (2.0~2.4): 1: (0.5~1.3).
The homologue of described naphthalene is the mixture of one or more in crude naphthalene, methyl naphthalene and betanaphthol.
Described hydroxy amino LOMAR PWA EINECS 246-676-2 is 1-amino-2-hydroxyl-4-LOMAR PWA EINECS 246-676-2,4-amino-3-hydroxyl-1-naphthalene sulfonic aicd, 5- The mixture of one or more in Amide-6-hydroxy-2-LOMAR PWA EINECS 246-676-2,6-amino-4-hydroxy-2-naphthalonesulfonic acid, consumption is naphthalene The 2~6% of homologue gross mass.
Described concentrated sulphuric acid: the mol ratio of the homologue of naphthalene is (1.1~1.8): 1, and described phosphoric acid consumption is concentrated sulphuric acid quality 4~12%.
Described sulfonation hydroxymethylphenol consumption is the 5~14% of the homologue gross mass of naphthalene, described formaldehyde: the homologue of naphthalene Mol ratio be (0.8~1.4): 1.
Compared with prior art, the present invention has features and a beneficial effect:
The present invention introduces substantial amounts of amino, hydroxyl and phosphate and phenyl ring in the molecular structure of water reducer, 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 Higher fluidity is also had, it is simple to transport and construct after 2h.
Preparation technology of the present invention is simple, easy to use, effective, practical.
Detailed description of the invention
Embodiments of the present invention are described in detail below, whereby to the present invention how application technology hands with specific embodiment Section solves technical problem, and the process that realizes reaching technique effect can fully understand and implement according to this.
Embodiment 1:
(1) preparation of sulfonation hydroxymethylphenol:
Put into 163.8 parts of phenol, 208.8 parts of sodium sulfitees and 266 parts of water in a kettle., be heated to 40 while stirring ~50 DEG C;The pH value adding 56.4 part of 32% liquid caustic soda regulation reaction system is 8~9;Temperature control drips 305 parts of formaldehyde, drips Cheng Zhongying controls rate of addition, makes system temperature be less than 70 DEG C;Drip complete post-heating to 80~90 DEG C and isothermal reaction 4~ 5h;Stop heating, be cooled to about 40 DEG C dischargings, obtain sulfonation hydroxymethylphenol A.
(2) a kind of modified high-thin arch dam naphthalene water reducer, its preparation process is as follows:
(1) sulfonation: put into 138 parts of crude naphthalenes in reactor and 28 parts of methyl naphtho-heating are melted to 130~135 DEG C, add Enter 145 part of 98% concentrated sulphuric acid, in 160 DEG C of sulfonating reactions 3~4h;
(2) hydrolysis: be cooled to 120 DEG C, adds 9.7 parts of phosphoric acid and 100 parts of water, hydrolyzes 1~2h;
(3) condensation: be cooled to 95 DEG C, add 10.8 parts of sulfonation hydroxymethylphenol A and 4.2 parts of 1-amino-2-hydroxyl-4-naphthalenes Sulfonic acid, is subsequently adding 95 parts of formaldehyde, carries out condensation reaction 3h~4h at 100~105 DEG C;
(4) neutralize: aforementioned condensation material proceeds to neutralize still and add 148 part of 32% liquid caustic soda and 236 parts of water, is neutralized by reactant It is 8~10 to pH value, i.e. obtains modified high-thin arch dam naphthalene water reducer.
Embodiment 2:
(1) preparation of sulfonation hydroxymethylphenol:
Put into 160.8 parts of phenol, 226.7 sodium sulfite and 299 parts of water in a kettle., be heated to 40~50 while stirring ℃;Temperature control drips 313.5 parts of formaldehyde, should control rate of addition, make system temperature be less than 70 DEG C during dropping;Drip Finish post-heating to 80~90 DEG C and isothermal reaction 4~5h;Stop heating, be cooled to about 40 DEG C dischargings, obtain sulfonation methylol Phenol B.
(2) a kind of modified high-thin arch dam naphthalene water reducer, its preparation process is as follows:
(1) sulfonation: put into 138 parts of crude naphthalenes in reactor and 28 parts of methyl naphtho-heating are melted to 130~135 DEG C, add Enter 145 part of 98% concentrated sulphuric acid, in 160 DEG C of sulfonating reactions 3~4h;
(2) hydrolysis: be cooled to 120 DEG C, adds 9.7 parts of phosphoric acid and 100 parts of water, hydrolyzes 1~2h;
(3) condensation: be cooled to 95 DEG C, add 19.9 parts of sulfonation hydroxymethylphenol B and 5.8 parts of 4-amino-3-hydroxyl-1-naphthalenes Sulfonic acid, is subsequently adding 95 parts of formaldehyde, carries out condensation reaction 3h~4h at 100~105 DEG C;
(4) neutralize: aforementioned condensation material proceeds to neutralize still and add 148 part of 32% liquid caustic soda and 239 parts of water, is neutralized by reactant It is 8~10 to pH value, i.e. obtains 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, its preparation process is as follows:
(1) sulfonation: put into 162 parts of industrial naphtho-heating in reactor and be melted to 130~135 DEG C, add 163.7 part 98% Concentrated sulphuric acid, in 160 DEG C of sulfonating reactions 3~4h;
(2) hydrolysis: be cooled to 120 DEG C, adds 8.2 parts of phosphoric acid and 100 parts of water, hydrolyzes 1~2h;
(3) condensation: be cooled to 95 DEG C, add 10.5 parts of sulfonation hydroxymethylphenol A and 5.7 parts of 1-amino-2-hydroxyl-4-naphthalenes Sulfonic acid, is subsequently adding 118 parts of formaldehyde, carries out condensation reaction 3~4h at 100~105 DEG C;
(4) neutralize: aforementioned condensation material proceeds to neutralize still and add 162 part of 32% liquid caustic soda and 245 parts of water, is neutralized by reactant It is 8~10 to pH value, i.e. obtains modified high-thin arch dam naphthalene water reducer.
Embodiment 4:
(1) preparation of sulfonation hydroxymethylphenol:
Put into 157 parts of phenol, 208.3 parts of sodium sulfitees and 254 parts of water in a kettle., be heated to while stirring 40~ 50℃;The pH value adding 60.7 part of 32% liquid caustic soda regulation reaction system is 8~9;Temperature control dropping, by 320 parts of formaldehyde, drips process In should control rate of addition, make system temperature be less than 70 DEG C;Drip complete post-heating to 80~90 DEG C and isothermal reaction 4~ 5h;Stop heating, be cooled to about 40 DEG C dischargings, obtain sulfonation hydroxymethylphenol C.
(2) a kind of modified high-thin arch dam naphthalene water reducer, its preparation process is as follows:
(1) sulfonation: put into 116 parts of crude naphthalenes in reactor and 52 parts of methyl naphtho-heating are melted to 130~135 DEG C, add Enter 174.5 part of 98% concentrated sulphuric acid, in 160 DEG C of sulfonating reactions 3~4h;
(2) hydrolysis: be cooled to 120 DEG C, adds 7.5 parts of phosphoric acid and 100 parts of water, hydrolyzes 1~2h;
(3) condensation: be cooled to 95 DEG C, add 22.7 parts of sulfonation hydroxymethylphenol C and 9.2 parts of 4-amino-3-hydroxyl-1-naphthalenes Sulfonic acid, is subsequently adding 111.3 parts of formaldehyde, carries out condensation reaction 3~4h at 100~105 DEG C;
(4) neutralize: aforementioned condensation material proceeds to neutralize still and add 146 part of 32% liquid caustic soda and 277 parts of water, is neutralized by reactant It is 8~10 to pH value, i.e. obtains modified high-thin arch dam naphthalene water reducer.
Embodiment 5:
(1) preparation of sulfonation hydroxymethylphenol:
Put into 150 parts of phenol, 196.8 parts of sodium pyrosulfite and 214 parts of water in a kettle., be heated to while stirring 40~ 50℃;The pH value adding 120.5 part of 32% liquid caustic soda regulation reaction system is 8~9;Temperature control drips 318.7 parts of formaldehyde, drips Cheng Zhongying controls rate of addition, makes system temperature be less than 70 DEG C;Drip complete post-heating to 80~90 DEG C and isothermal reaction 4~ 5h;Stop heating, be cooled to about 40 DEG C dischargings, obtain sulfonation hydroxymethylphenol D.
(2) a kind of modified high-thin arch dam naphthalene water reducer, its preparation process is as follows:
(1) sulfonation: put into 120 parts of crude naphthalenes and 55 parts of betanaphthols in reactor and heating is melted to 130~135 DEG C, add Enter 148.7 part of 98% concentrated sulphuric acid, in 160 DEG C of sulfonating reactions 3~4h;
(2) hydrolysis: be cooled to 120 DEG C, adds 15.2 parts of phosphoric acid and 100 parts of water, hydrolyzes 1~2h;
(3) condensation: be cooled to 95 DEG C, add 15.8 parts of sulfonation hydroxymethylphenol D and 5.3 parts of 5-Amide-6-hydroxy-2-naphthalenes Sulfonic acid, is subsequently adding 104.5 parts of formaldehyde, carries out condensation reaction 3~4h at 100~105 DEG C;
(4) neutralize: aforementioned condensation material proceeds to neutralize still and add 149 part of 32% liquid caustic soda and 258 parts of water, is neutralized by reactant It is 8~10 to pH value, i.e. obtains 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, its preparation process is as follows:
(1) sulfonation: put into 128 parts of crude naphthalenes and 46 parts of betanaphthols in reactor and heating is melted to 130~135 DEG C, add Enter 150 part of 98% concentrated sulphuric acid, in 160 DEG C of sulfonating reactions 3~4h;
(2) hydrolysis: be cooled to 120 DEG C, adds 10.4 parts of phosphoric acid and 100 parts of water, hydrolyzes 1~2h;
(3) condensation: be cooled to 95 DEG C, add 17.4 parts of sulfonation hydroxymethylphenol D and 7.0 parts of 6-amino-4-hydroxy-2-naphthalenes Sulfonic acid, is subsequently adding 132 parts of formaldehyde, carries out condensation reaction 3~4h at 100~105 DEG C;
(4) neutralize: aforementioned condensation material proceeds to neutralize still and add 142 part of 32% liquid caustic soda and 250 parts of water, is neutralized by reactant It is 8~10 to pH value, i.e. obtains modified high-thin arch dam naphthalene water reducer.
Comparative example:
The synthesis of a kind of common naphthalene water reducer comprises the following steps:
(1) sulfonation: put into the heating of 162 parts of industrial naphtho-s in reactor and be melted to 130~135 DEG C, add 170 part 98% dense Sulphuric acid, in 160 DEG C of sulfonating reactions 3~4h;
(2) hydrolysis: be cooled to 120 DEG C, adds 100 parts of water, hydrolyzes 1~2h;
(3) condensation: be cooled to 95 DEG C, add 110 parts of formalins, carry out condensation reaction 3~4h at 100 DEG C;
(4) neutralize: aforementioned condensation material proceeds to neutralize still and add 140 part of 32% liquid caustic soda and 243 parts of water, is neutralized by reactant It is 8~10 to pH value, i.e. obtains product.
Application Example 1:
In order to evaluate the performance of the modified high-thin arch dam naphthalene water reducer of the present invention, according to GB/T8077-2012 " outside concrete Add agent homogeneity test method " carry out the test of different flowing degree of net paste of cement.In test three kinds of cement be respectively reference cement, The crane woods P O that Carnis Rapanae thomasianae P O 42.5 cement of Chinese cement Co., Ltd., Factory product and Jiangsu He Lin Cement Co., Ltd produce 42.5 cement;Water reducer, in addition to above-described embodiment and comparative example, also selects the FDN naphthalene water reducer of Shandong factory to carry out right Ratio, volume is 0.75% (counting on the basis of the weight of cement after folding is solid), and result of the test is shown in Table 1.
The flowing degree of net paste of cement of the different naphthalene water reducer of table 1
From table 1 result, the modified high-thin arch dam naphthalene water reducer of present invention pulp flowage in three kinds of cement Spend the common naphthalene water reducer that especially gradual loss is totally better than in two kinds of comparative examples.
Application Example 2:
According to the relevant regulations of high efficiency water reducing agent in GB 8076-2008 " concrete admixture ", evaluate and mix changing of the present invention The water-reducing rate of concrete, air content, setting time and the comprcssive strength of property high-thin arch dam naphthalene water reducer.Test uses reference water Mud, modulus of fineness is the medium sand of 2.6, the rubble of 5~20mm continuous gradings, and concrete mix is cement: sand: stone=330: 768:1152, adjusts water consumption and makes fresh concrete initial slump be 80mm ± 10mm, and the volume of water reducer is cement weight 0.75% (folding solid).Result of the test is shown in Table 2.
The concrete performance of the present invention mixed by table 2
From table 2 result, when the modified high-thin arch dam naphthalene water reducer volume of the present invention is 0.75% water-reducing rate up to More than 23%, the most common naphthalene water reducer;Air content is compared with blank group and is only had a small increase, for non-research work of air entrained type diminishing Agent;Setting time has compared a certain degree of prolongation with common naphthalene water reducer, but for 7d, 28d comprcssive strength without bad shadow Ring.
Application Example 3:
According to the relevant regulations of pumping admixture in GB 8076-2008 " concrete admixture ", the evaluation present invention's is modified high Protect air content, setting time, the slump and 1h rheological parameters' change with time after the naphthalene water reducer that collapses is re-dubbed pumping admixture and mixes concrete Amount and comprcssive strength.Test uses reference cement, and modulus of fineness is the medium sand of 2.6, the rubble of 5~20mm continuous gradings, coagulation Soil match ratio is cement: sand: stone: water=360:864:1056:185;Pumping admixture volume is 1.2%, and formula is naphthalene water reducer: Rosin air entraining agent: sodium gluconate: water=0.4:0.03:0.03:0.54, result of the test see table 3.
The concrete performance after the pumping admixture that the present invention is re-dubbed mixed by table 3
From table 3 result, after being re-dubbed pumping admixture with the modified high-thin arch dam naphthalene water reducer of the present invention, mix concrete, Comparing with normal concrete, air content and 7d, 28d comprcssive strength are substantially unaffected, and concrete slump and the degree of expansion that collapses, especially It is that 1h rheological parameters' change with time amount is obviously reduced, and is more beneficial for concrete long-distance transportation and pumping construction.
Although the present invention is described by embodiment, but embodiment is not used for limiting the present invention.Art technology Personnel in the scope of the spirit of the present invention, can make the adjustment of various deformation and improvement, such as component ratio or time range, 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 as the criterion by identical with claims hereof or equivalent the protection domain that defined of technical characteristic.

Claims (7)

1. the preparation method of a modified high-thin arch dam naphthalene water reducer, it is characterised in that comprise the following steps:
Step one, the preparation of sulfonation hydroxymethylphenol:
Put into a certain amount of phenol, sulfonating agent and water in a kettle., under being stirred continuously, be heated to 40~50 DEG C;Add 32% The pH value of liquid caustic soda regulation reaction system is 8~9;Dropping formaldehyde, should control rate of addition during dropping, make system temperature not More than 70 DEG C;Drip complete post-heating to 80~90 DEG C and isothermal reaction 4~5h;Stop heating, be cooled to about 40 DEG C dischargings, Obtain sulfonation hydroxymethylphenol;
Step 2, the preparation of modified high-thin arch dam naphthalene water reducer:
(1) sulfonation: the homologue the heating that put into naphthalene in reactor are melted to 130~135 DEG C, add 98% concentrated sulphuric acid, 150 ~170 DEG C of sulfonating reactions 3~4h, obtain sulfonation material;
(2) hydrolysis: be cooled to 100~130 DEG C, adds a certain amount of phosphoric acid and water, hydrolyzes 1~2h;
(3) condensation: be cooled to 90~105 DEG C through the material of hydrolysing step, adds sulfonation hydroxymethylphenol and hydroxy amino naphthalene sulphur Acid, adds formaldehyde, carries out condensation reaction 3~4h at 100~105 DEG C;
(4) neutralize: aforementioned condensation material proceeds to neutralize still and add 32% liquid caustic soda and water, and it is 8~10 that reactant is neutralized to pH value, I.e. obtain described modified high-thin arch dam naphthalene water reducer.
The preparation method of modified high-thin arch dam naphthalene water reducer the most according to claim 1, it is characterised in that: described sulfonating agent For the mixture of one or more in sodium sulfite, sodium sulfite or sodium pyrosulfite.
The preparation method of modified high-thin arch dam naphthalene water reducer the most according to claim 1, it is characterised in that: described formaldehyde: Phenol: the mol ratio of sulfonating agent is (2.0~2.4): 1:(0.5~1.3).
The preparation method of modified high-thin arch dam naphthalene water reducer the most according to claim 1, it is characterised in that: described naphthalene same Be thing be the mixture of one or more in crude naphthalene, methyl naphthalene and betanaphthol.
The preparation method of modified high-thin arch dam naphthalene water reducer the most according to claim 1, it is characterised in that: described amino hydroxyl Base LOMAR PWA EINECS 246-676-2 is 1-amino-2-hydroxyl-4-LOMAR PWA EINECS 246-676-2,4-amino-3-hydroxyl-1-naphthalene sulfonic aicd, 5-Amide-6-hydroxy-2-naphthalene sulphur Acid, the mixture of one or more in 6-amino-4-hydroxy-2-naphthalonesulfonic acid, consumption be the homologue gross mass of naphthalene 2~ 6%.
The preparation method of modified high-thin arch dam naphthalene water reducer the most according to claim 1, it is characterised in that: described dense sulfur Acid: the mol ratio of the homologue of naphthalene is (1.1~1.8): 1, and described phosphoric acid consumption is the 4~12% of concentrated sulphuric acid quality.
The preparation method of modified high-thin arch dam naphthalene water reducer the most according to claim 1, it is characterised in that: described sulfonation hydroxyl Methylphenol consumption is the 5~14% of the homologue gross mass of naphthalene, described formaldehyde: the mol ratio of the homologue of naphthalene be (0.8~ 1.4):1。
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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
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