CN112125564B - Naphthalene water reducer - Google Patents

Naphthalene water reducer Download PDF

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CN112125564B
CN112125564B CN202010541954.9A CN202010541954A CN112125564B CN 112125564 B CN112125564 B CN 112125564B CN 202010541954 A CN202010541954 A CN 202010541954A CN 112125564 B CN112125564 B CN 112125564B
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naphthalene
sodium
water
parts
sulfonate
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CN112125564A (en
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董翠平
马丽涛
彭城
杨道顺
李曼
乔琼琼
朱海涛
王超
王冰
欧大康
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Anhui Xin Solid Environmental Co ltd
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Anhui Xin Solid Environmental Co ltd
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    • 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
    • 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

Abstract

The invention relates to the technical field of building materials, in particular to a naphthalene water reducer. The naphthalene water reducing agent is prepared from naphthalene sulfonate, naphthalene oil, sulfonating agent, aldehyde compound, pH regulator and water, wherein the naphthalene sulfonate is naphthalene sulfonate containing amino or hydroxyl, and the sulfonating agent is a mixture of 98wt% of concentrated sulfuric acid, sodium pyrosulfite and sodium sulfite. The invention effectively improves the quality stability of the water reducing agent in the production process by doping two naphthalene sulfonates with specific proportion in the raw materials and adopting the sulfonating agent with specific proportion, and the invention effectively enhances the cohesiveness of aggregate and cement paste in concrete and improves the water reducing rate of the water reducing agent when being used in concrete.

Description

Naphthalene water reducer
Technical Field
The invention relates to the technical field of building materials, in particular to a naphthalene water reducer.
Background
The naphthalene water reducing agent is a concrete additive which is most widely used at present, has the characteristics of high water reducing rate, no air entraining, small influence on the setting time, relatively good adaptability to cement, capability of being used in combination with other additives, relatively low price and capability of being frequently used for preparing concrete with large fluidity, high strength and high performance. The preparation process of the naphthalene water reducer mainly comprises the steps of sulfonation, hydrolysis, condensation, neutralization, filtration, drying and the like, wherein the quality of sulfonation reaction control directly influences the type and content of generated naphthalene sulfonate, and greatly influences the quality of a product after condensation.
The naphthalene oil is coal tar distillate with distillation range of 210-230 ℃ in the process of preparing industrial naphthalene or refined naphthalene, wherein the naphthalene content is 40-95%, and the naphthalene oil also contains a small amount of phenols, indole and other compounds with complex components. Because the boiling points are close, the components are complex and difficult to separate and purify, and secondary pollution is caused to the environment.
In the conventional sulfonation reaction, besides beta-naphthalenesulfonic acid, alpha-naphthalenesulfonic acid with variable amount is usually generated, which is not beneficial to the subsequent condensation reaction, therefore, water needs to be added for removing the alpha-naphthalenesulfonic acid through hydrolysis reaction, and simultaneously sulfuric acid is generated, on one hand, the generation amount of the alpha-naphthalenesulfonic acid is difficult to estimate, the water addition amount is difficult to control, the acidity and the sulfonation degree of a final system are difficult to control, on the other hand, the sulfonation process is reversible reaction, the generation of the sulfuric acid influences the balance of the system, and further, the alpha-naphthalenesulfonic acid is likely to be generated, and the cycle is repeated, the quality of the water reducer is difficult to control in the actual production process, and the quality of the water reducer produced in different batches is not stable.
Disclosure of Invention
In order to solve the technical problems, the invention provides a naphthalene water reducer in a first aspect, wherein the raw materials of the naphthalene water reducer comprise naphthalene sulfonate, naphthalene oil, a sulfonating agent, an aldehyde compound, a pH regulator and water.
In a preferred embodiment of the present invention, the naphthalene sulfonate is at least one selected from the group consisting of sodium 7-amino-2-naphthalene sulfonate, sodium 1-hydroxynaphthalene-5 sulfonate, sodium 2-hydroxy-7-naphthalene sulfonate, sodium 2, 3-dihydroxynaphthalene-6-sulfonate, sodium 2, 8-dihydroxynaphthalene-6-sulfonate, and sodium 4-amino-5-hydroxynaphthalene-2, 7-disulfonate.
As a preferable technical scheme, the naphthalene sulfonate accounts for 1-5% of the total mass of the naphthalene water reducer.
As a preferable technical scheme of the invention, the mass ratio of the naphthalene oil to the naphthalene sulfonate is (5-7): 1.
as a preferable technical scheme of the invention, the mass ratio of the sulfonating agent to the naphthalene oil is (1-1.6): 1.
As a preferable technical scheme, the mass ratio of the sulfonating agent to the naphthalene oil is 1.4:1.
as a preferred technical scheme of the invention, the sulfonating agent comprises 98wt% concentrated sulfuric acid.
As a preferable technical scheme of the invention, the sulfonating agent further comprises sodium metabisulfite and sodium sulfite.
As a preferable technical scheme of the invention, the mass ratio of 98wt% of concentrated sulfuric acid, sodium metabisulfite and sodium sulfite in the sulfonating agent is 10: (0.3-0.5): (0.2-0.5).
As a preferable technical scheme of the invention, the pH regulator is 32wt% sodium hydroxide solution or 2mol/L sulfuric acid.
The second aspect of the present invention provides a preparation method of the naphthalene water reducing agent, including the following steps: adding naphthalene sulfonate and naphthalene oil into a reaction container, heating, then dropwise adding a sulfonating agent, and preserving heat; then cooling, adding water and preserving heat; then dripping aldehyde compounds, and preserving heat; and then cooling to below 80 ℃, and adding a pH regulator for neutralization treatment to obtain the naphthalene water reducer.
Has the beneficial effects that: the invention provides a naphthalene water reducer, which comprises naphthalene sulfonate, naphthalene oil, a sulfonating agent, an aldehyde compound, a pH regulator and water, wherein the naphthalene sulfonate is naphthalene sulfonate containing amino or hydroxyl, and the sulfonating agent is a mixture of 98wt% of concentrated sulfuric acid, sodium metabisulfite and sodium sulfite.
Detailed Description
The disclosure may be understood more readily by reference to the following detailed description of preferred embodiments of the invention and the examples included therein. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In case of conflict, the present specification, including definitions, will control.
The terms "comprises," "comprising," "including," "has," "having," "contains," or any other variation thereof, as used herein, are intended to cover a non-exclusive inclusion. For example, a composition, step, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, step, method, article, or apparatus.
When an amount, concentration, or other value or parameter is expressed as a range, preferred range, or range defined by a list of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. For example, when the range "1 to 5" is disclosed, the described range should be construed as including the ranges "1 to 4", "1 to 3", "1 to 2 and 4 to 5", "1 to 3 and 5", and the like. When a range of values is described herein, unless otherwise stated, the range is intended to include the endpoints thereof and all integers and fractions within the range.
In addition, the indefinite articles "a" and "an" preceding an element or component of the invention are not intended to limit the number requirement (i.e., the number of occurrences) of the element or component. Thus, "a" or "an" should be read to include one or at least one, and the singular form of an element or component also includes the plural unless the number clearly indicates the singular.
In order to solve the technical problems, the invention provides a naphthalene water reducer in a first aspect, wherein the raw materials of the naphthalene water reducer comprise naphthalene sulfonate, naphthalene oil, a sulfonating agent, an aldehyde compound, a pH regulator and water.
In some embodiments, the naphthalene sulfonate is selected from at least one of sodium 7-amino-2-naphthalene sulfonate (CAS number: 5412-82-8), sodium 1-hydroxynaphthalene-5 sulfonate (CAS number: 79873-34-0), sodium 2-hydroxy-7-naphthalene sulfonate (CAS number: 135-55-7), sodium 2, 3-dihydroxynaphthalene-6-sulfonate (CAS number: 135-53-5), sodium 2, 8-dihydroxynaphthalene-6-sulfonate (CAS number: 83732-66-5), sodium 4-amino-5-hydroxynaphthalene-2, 7-disulfonate (CAS number: 343321-59-5); preferably, the naphthalene sulfonate is a compound of 2, 3-dihydroxy naphthalene-6-sodium sulfonate and 4-amino-5-hydroxy naphthalene-2, 7-sodium disulfonate, and the weight ratio of the two is 1:2.
in some embodiments, the naphthalene sulfonate accounts for 1-5% of the total mass of the naphthalene water reducer; preferably, the naphthalene sulfonate accounts for 2.5% of the total mass of the naphthalene water reducer.
In some embodiments, the mass ratio of the naphthalene oil to the naphthalene sulfonate is (5-7): 1; preferably, the mass ratio of the naphthalene oil to the naphthalene sulfonate is 6:1. the naphthalene oil can be a raw material on the market, and a product with the naphthalene content of 45-95% can be selected.
In some embodiments, the mass ratio of the sulfonating agent to naphthalene oil is (1 to 1.6): 1; preferably, the mass ratio of the sulfonating agent to the naphthalene oil is 1.4:1.
in some embodiments, the sulfonating agent comprises 98wt% concentrated sulfuric acid.
In a preferred embodiment, the sulfonating agent further comprises sodium metabisulfite, sodium sulfite.
In a more preferred embodiment, the mass ratio of 98wt% concentrated sulfuric acid, sodium metabisulfite and sodium sulfite in the sulfonating agent is 10: (0.3-0.5): (0.2-0.5); preferably, the mass ratio of 98wt% concentrated sulfuric acid, sodium metabisulfite and sodium sulfite in the sulfonating agent is 10:0.4:0.5.
in some embodiments, the pH adjusting agent is 32wt% sodium hydroxide solution or 2mol/L sulfuric acid.
The aldehyde compound is not particularly limited in the present invention, and includes, but is not limited to: formaldehyde, acetaldehyde, propionaldehyde; preferably, the aldehyde compound in the present invention is formaldehyde.
In the process of preparing the naphthalene water reducer by taking naphthalene or naphthalene homologues as raw materials, the raw materials are required to be sulfonated to generate sulfonic acid derivatives, alpha-naphthalenesulfonic acid is inevitably generated in the process, and alpha-naphthalenesulfonate formaldehyde condensate has no obvious water reducing effect in cement concrete, so water is usually required to be added for removing the sulfonic acid derivatives through hydrolysis reaction.
The applicant unexpectedly finds that when 1-5 wt% of naphthalene sulfonate is doped into the raw material, the quality of the generated water reducer in different batches is more stable, and presumably, the naphthalene sulfonate with specific content is doped, so that the generation of alpha-naphthalene sulfonic acid in the sulfonation process can be avoided, a series of problems of acidity, sulfonation degree, reaction balance and the like caused by the generation of sulfuric acid in the hydrolysis process are avoided, the process parameters of each batch in the whole water reducer preparation process are easy to accurately monitor and control, and the stability of the product quality is ensured. In addition, the applicant has surprisingly found that the raw materials are mixed with the raw materials in a mass ratio of 1:2, 3-dihydroxy naphthalene-6-sodium sulfonate and 4-amino-5-hydroxy naphthalene-2, 7-sodium disulfonate, the generated water reducing agent is used in concrete, the cohesiveness of concrete aggregate and cement paste is better, the concrete is more uniform, honeycomb or cavity phenomenon can not occur after vibrating, presumably due to active groups such as hydroxyl and amino in the molecular structures of the 2, 3-dihydroxy naphthalene-6-sodium sulfonate and the 4-amino-5-hydroxy naphthalene-2, 7-sodium disulfonate, the cohesiveness of the aggregate and the cement paste is enhanced, the steric effect generated by benzene rings is enhanced, and the dispersibility among mixed materials is enhanced, so that the cohesiveness of the materials in the concrete is good, and the materials are uniformly mixed.
In order to control the concentration of 98wt% of concentrated sulfuric acid in the sulfonating agent in the invention to ensure stable sulfonation speed, the applicant compounds sodium metabisulfite and sodium sulfite as sulfonating agents, so that the sulfonation speed is stable, the water reducing rate of the water reducing agent is further improved unexpectedly, and the probable reason is presumed that sodium ions have the function of refining crystal particles, and the cement particles can be prevented from forming flocculent structures to lock free water.
The second aspect of the present invention provides a method for producing the above-mentioned naphthalene based water reducing agent, comprising the steps of: adding naphthalene sulfonate and naphthalene oil into a reaction container, heating, then dropwise adding a sulfonating agent, and preserving heat; then cooling, adding water and preserving heat; then dripping aldehyde compounds, and preserving heat; and then cooling to below 80 ℃, and adding a pH regulator for neutralization treatment to obtain the naphthalene water reducer.
In a preferred embodiment, the preparation method comprises the following steps: adding naphthalene sulfonate and naphthalene oil into a reaction container, heating to 150 ℃, then dropwise adding a sulfonating agent, keeping the temperature for 2.5 hours after dropwise adding within 30min, then cooling to 120 ℃, adding water, and keeping the temperature for 0.2 hour; then dripping aldehyde compound, controlling the dripping speed, keeping the temperature for 2h after dripping within 1.5-3.5 h (wherein in the processes of adding the aldehyde compound, keeping the temperature, reacting and the like, if the material is particularly viscous, a small amount of water is added for many times); then cooling to below 80 ℃, adding a pH regulator to neutralize to a pH value within a range of 7-9, and obtaining the naphthalene water reducer.
The naphthalene oil (the naphthalene content is 82%) is derived from fraction residue at 210-230 ℃ generated in the process of preparing refined naphthalene from industrial naphthalene of Shouxian Ward chemical technology Co., ltd; the formaldehyde content is 35-37 wt%.
Examples
Example 1
The embodiment provides a naphthalene water reducer which comprises, by weight, 10 parts of naphthalene sulfonate, 60 parts of naphthalene oil, 84 parts of a sulfonating agent, 100 parts of formaldehyde and 30 parts of water, wherein the naphthalene sulfonate is prepared from the following raw materials in a weight ratio of 1:2, 3-dihydroxy naphthalene-6-sodium sulfonate and 4-amino-5-hydroxy naphthalene-2, 7-sodium disulfonate, wherein the sulfonating agent is a mixture of 10:0.4:0.5 of a mixture of 98% by weight of concentrated sulfuric acid, sodium metabisulfite and sodium sulfite.
The embodiment also provides a preparation method of the naphthalene water reducer, which comprises the following steps: adding naphthalene sulfonate and naphthalene oil into a reaction container, heating to 150 ℃, then dropwise adding a sulfonating agent, keeping the temperature for 2.5 hours after dropwise adding within 30min, then cooling to 120 ℃, adding water, and keeping the temperature for 0.2 hour; then dripping formaldehyde, and keeping the temperature for 2 hours; then cooling to below 80 ℃, adding 32wt% of sodium hydroxide solution to neutralize to a pH value of 7-9, and obtaining the naphthalene water reducer.
Example 2
The embodiment provides a naphthalene water reducer which comprises, by weight, 70 parts of naphthalene oil, 84 parts of a sulfonating agent, 100 parts of formaldehyde and 30 parts of water, wherein the sulfonating agent is a mixture of, by weight, 10:0.4:0.5 98wt% of concentrated sulfuric acid, sodium metabisulfite, sodium sulfite.
The embodiment also provides a preparation method of the naphthalene water reducer, which comprises the following steps: adding naphthalene oil into a reaction vessel, heating to 150 ℃, then dropwise adding a sulfonating agent, keeping the temperature for 2.5 hours after dropwise adding within 30 minutes, then cooling to 120 ℃, adding water, and keeping the temperature for 0.2 hour; then dripping formaldehyde, and keeping the temperature for 2 hours; then cooling to below 80 ℃, adding 32wt% of sodium hydroxide solution to neutralize to a pH value of 7-9, and obtaining the naphthalene water reducer.
Example 3
The embodiment provides a naphthalene water reducer which comprises, by weight, 10 parts of naphthalene sulfonate, 60 parts of naphthalene oil, 84 parts of a sulfonating agent, 100 parts of formaldehyde and 30 parts of water, wherein the naphthalene sulfonate is prepared from the following raw materials in a weight ratio of 1:2 (CAS number: 1322-93-6) and butyl sodium naphthalene sulfonate (CAS number: 25638-17-9), wherein the sulfonating agent is a mixture of 10:0.4:0.5 of a mixture of concentrated sulfuric acid, sodium metabisulfite, sodium sulfite at 98% by weight.
The embodiment also provides a preparation method of the naphthalene water reducer, which comprises the following steps: adding naphthalene sulfonate and naphthalene oil into a reaction vessel, heating to 150 ℃, then dropwise adding a sulfonating agent, keeping the temperature for 2.5h after dropwise adding within 30min, then cooling to 120 ℃, adding water, and keeping the temperature for 0.2h; then dripping formaldehyde, and preserving the heat for 2 hours; then cooling to below 80 ℃, adding 32wt% of sodium hydroxide solution to neutralize to a pH value of 7-9, and obtaining the naphthalene water reducer.
Example 4
The embodiment provides a naphthalene water reducer which comprises, by weight, 10 parts of naphthalene sulfonate, 60 parts of naphthalene oil, 84 parts of a sulfonating agent, 100 parts of formaldehyde and 30 parts of water, wherein the naphthalene sulfonate is prepared from the following raw materials in a weight ratio of 1:2, the sulfonating agent is a compound of 7-amino-2-sodium naphthalene sulfonate and 2-hydroxy-7-sodium naphthalene sulfonate in a weight ratio of 10:0.4:0.5 of a mixture of 98% by weight of concentrated sulfuric acid, sodium metabisulfite and sodium sulfite.
The embodiment also provides a preparation method of the naphthalene water reducer, which comprises the following steps: adding naphthalene sulfonate and naphthalene oil into a reaction container, heating to 150 ℃, then dropwise adding a sulfonating agent, keeping the temperature for 2.5 hours after dropwise adding within 30min, then cooling to 120 ℃, adding water, and keeping the temperature for 0.2 hour; then dripping formaldehyde, and keeping the temperature for 2 hours; then cooling to below 80 ℃, adding 32wt% of sodium hydroxide solution to neutralize to a pH value of 7-9, and obtaining the naphthalene water reducer.
Example 5
The embodiment provides a naphthalene water reducer which comprises, by weight, 10 parts of naphthalene sulfonate, 60 parts of naphthalene oil, 84 parts of a sulfonating agent, 100 parts of formaldehyde and 30 parts of water, wherein the naphthalene sulfonate is 2, 3-dihydroxy naphthalene-6-sodium sulfonate, and the sulfonating agent is a mixture of, by weight, 10:0.4:0.5 of a mixture of 98% by weight of concentrated sulfuric acid, sodium metabisulfite and sodium sulfite.
The embodiment also provides a preparation method of the naphthalene water reducer, which comprises the following steps: adding naphthalene sulfonate and naphthalene oil into a reaction container, heating to 150 ℃, then dropwise adding a sulfonating agent, keeping the temperature for 2.5 hours after dropwise adding within 30min, then cooling to 120 ℃, adding water, and keeping the temperature for 0.2 hour; then dripping formaldehyde, and preserving the heat for 2 hours; then cooling to below 80 ℃, adding 32wt% of sodium hydroxide solution to neutralize to a pH value of 7-9, and obtaining the naphthalene water reducer.
Example 6
The embodiment provides a naphthalene water reducer which comprises, by weight, 10 parts of naphthalene sulfonate, 60 parts of naphthalene oil, 84 parts of a sulfonating agent, 100 parts of formaldehyde and 30 parts of water, wherein the naphthalene sulfonate is sodium 4-amino-5-hydroxynaphthalene-2, 7-disulfonate, and the sulfonating agent is prepared from the following raw materials in a weight ratio of 10:0.4:0.5 of a mixture of concentrated sulfuric acid of 98% by weight, sodium metabisulfite, sodium sulfite.
The embodiment also provides a preparation method of the naphthalene water reducer, which comprises the following steps: adding naphthalene sulfonate and naphthalene oil into a reaction vessel, heating to 150 ℃, then dropwise adding a sulfonating agent, keeping the temperature for 2.5h after dropwise adding within 30min, then cooling to 120 ℃, adding water, and keeping the temperature for 0.2h; then dripping formaldehyde, and preserving the heat for 2 hours; then cooling to below 80 ℃, adding 32wt% of sodium hydroxide solution to neutralize to a pH value within a range of 7-9, and obtaining the naphthalene water reducer.
Example 7
The embodiment provides a naphthalene water reducer which comprises, by weight, 50 parts of naphthalene sulfonate, 60 parts of naphthalene oil, 84 parts of a sulfonating agent, 100 parts of formaldehyde and 30 parts of water, wherein the naphthalene sulfonate is prepared from the following raw materials in a weight ratio of 1:2, 3-dihydroxy naphthalene-6-sodium sulfonate and 4-amino-5-hydroxy naphthalene-2, 7-sodium disulfonate, wherein the sulfonating agent is a mixture of 10:0.4:0.5 of a mixture of 98% by weight of concentrated sulfuric acid, sodium metabisulfite and sodium sulfite.
The embodiment also provides a preparation method of the naphthalene water reducer, which comprises the following steps: adding naphthalene sulfonate and naphthalene oil into a reaction vessel, heating to 150 ℃, then dropwise adding a sulfonating agent, keeping the temperature for 2.5h after dropwise adding within 30min, then cooling to 120 ℃, adding water, and keeping the temperature for 0.2h; then dripping formaldehyde, and keeping the temperature for 2 hours; then cooling to below 80 ℃, adding 32wt% of sodium hydroxide solution to neutralize to a pH value of 7-9, and obtaining the naphthalene water reducer.
Example 8
The embodiment provides a naphthalene water reducer which comprises, by weight, 5 parts of naphthalene sulfonate, 60 parts of naphthalene oil, 84 parts of a sulfonating agent, 100 parts of formaldehyde and 30 parts of water, wherein the naphthalene sulfonate is prepared from the following raw materials in a weight ratio of 1:2, 3-dihydroxy naphthalene-6-sodium sulfonate and 4-amino-5-hydroxy naphthalene-2, 7-sodium disulfonate, wherein the sulfonating agent is a mixture of 10:0.4:0.5 of a mixture of 98% by weight of concentrated sulfuric acid, sodium metabisulfite and sodium sulfite.
The embodiment also provides a preparation method of the naphthalene water reducer, which comprises the following steps: adding naphthalene sulfonate and naphthalene oil into a reaction vessel, heating to 150 ℃, then dropwise adding a sulfonating agent, keeping the temperature for 2.5h after dropwise adding within 30min, then cooling to 120 ℃, adding water, and keeping the temperature for 0.2h; then dripping formaldehyde, and keeping the temperature for 2 hours; then cooling to below 80 ℃, adding 32wt% of sodium hydroxide solution to neutralize to a pH value within a range of 7-9, and obtaining the naphthalene water reducer.
Example 9
The embodiment provides a naphthalene water reducer which comprises, by weight, 10 parts of naphthalene sulfonate, 60 parts of naphthalene oil, 84 parts of sulfonating agent, 100 parts of formaldehyde and 30 parts of water, wherein the naphthalene sulfonate is a mixture of, by weight, 1:2, 3-dihydroxy naphthalene-6-sodium sulfonate and 4-amino-5-hydroxy naphthalene-2, 7-sodium disulfonate, wherein the sulfonating agent is 98wt% of concentrated sulfuric acid.
The embodiment also provides a preparation method of the naphthalene water reducer, which comprises the following steps: adding naphthalene sulfonate and naphthalene oil into a reaction vessel, heating to 150 ℃, then dropwise adding a sulfonating agent, keeping the temperature for 2.5h after dropwise adding within 30min, then cooling to 120 ℃, adding water, and keeping the temperature for 0.2h; then dripping formaldehyde, and preserving the heat for 2 hours; then cooling to below 80 ℃, adding 32wt% of sodium hydroxide solution to neutralize to a pH value of 7-9, and obtaining the naphthalene water reducer.
Example 10
The embodiment provides a naphthalene water reducer which comprises, by weight, 10 parts of naphthalene sulfonate, 60 parts of naphthalene oil, 84 parts of sulfonating agent, 100 parts of formaldehyde and 30 parts of water, wherein the naphthalene sulfonate is a mixture of, by weight, 1:2, 3-dihydroxy naphthalene-6-sodium sulfonate and 4-amino-5-hydroxy naphthalene-2, 7-sodium disulfonate, wherein the sulfonating agent is a mixture of 10:0.4 of a mixture of 98% by weight of concentrated sulfuric acid and sodium metabisulfite.
The embodiment also provides a preparation method of the naphthalene water reducer, which comprises the following steps: adding naphthalene sulfonate and naphthalene oil into a reaction container, heating to 150 ℃, then dropwise adding a sulfonating agent, keeping the temperature for 2.5 hours after dropwise adding within 30min, then cooling to 120 ℃, adding water, and keeping the temperature for 0.2 hour; then dripping formaldehyde, and keeping the temperature for 2 hours; then cooling to below 80 ℃, adding 32wt% of sodium hydroxide solution to neutralize to a pH value of 7-9, and obtaining the naphthalene water reducer.
Example 11
The embodiment provides a naphthalene water reducer which comprises, by weight, 10 parts of naphthalene sulfonate, 60 parts of naphthalene oil, 84 parts of a sulfonating agent, 100 parts of formaldehyde and 30 parts of water, wherein the naphthalene sulfonate is prepared from the following raw materials in a weight ratio of 1:2, 3-dihydroxy naphthalene-6-sodium sulfonate and 4-amino-5-hydroxy naphthalene-2, 7-sodium disulfonate, wherein the sulfonating agent is a mixture of 10:0.4:0.5 of a mixture of 98% by weight of concentrated sulfuric acid, sodium metabisulfite and sodium sulfite.
The embodiment also provides a preparation method of the naphthalene water reducer, which comprises the following steps: adding naphthalene oil into a reaction vessel, heating to 150 ℃, then dropwise adding a sulfonating agent, keeping the temperature for 3 hours after dropwise adding within 30min, then cooling to 120 ℃, adding water, keeping the temperature for 0.2 hour, then adding naphthalene sulfonate, and stirring for 0.3 hour; then formaldehyde is dripped, and the temperature is kept for 2.5h; and then cooling to below 80 ℃, adding 32wt% of sodium hydroxide solution for neutralization to a pH value within a range of 7-9, and thus obtaining the naphthalene water reducer.
Evaluation of Properties
The components and the method in the embodiment are respectively adopted to prepare three batches of water reducing agents repeatedly for three times, the water reducing rate of concrete doped with the water reducing agents prepared in different batches in the embodiment of the invention is evaluated according to the relevant regulations of the water reducing agents in GB 8076-2008 'concrete admixture', the cohesiveness of aggregate and cement paste in the concrete stirring process and whether the phenomenon of honeycomb or cavity appears after vibration are observed at the same time, the cohesiveness is divided into three grades of A, B and C, wherein A is the optimal, and the quality stability of the water reducing agents is evaluated according to the results of the three batches. The test adopts standard cement, the mixing amount of the water reducing agent is 0.75 percent (broken and fixed) of the weight of the cement, and the test results are shown in the following table.
TABLE 1 Water reducing Property test results
Figure BDA0002539206530000091
Figure BDA0002539206530000101
TABLE 2 results of the cohesion property test
Figure BDA0002539206530000102
According to the results in the table, the naphthalene water reducer provided by the invention is easy to control batch quality in the production process, has better cohesiveness when used in concrete mixtures, and effectively improves the water reducing rate; specifically, it can be seen from the results of comparative example 1 and example 2 that the present invention can improve the stability of the quality of the batch product by incorporating a specific naphthalene sulfonate into the raw material; the results of comparative examples 3 to 8 show that the cohesiveness of aggregate and cement paste in concrete is simultaneously enhanced by the naphthalene sulfonate with specific type and content; as can be seen from the results of comparative examples 9 and 10, the present invention can further improve the water reducing rate of the water reducing agent by using a specific sulfonating agent.
The foregoing examples are merely illustrative and serve to explain some of the features of the method of the present invention. The appended claims are intended to claim as broad a scope as is contemplated, and the examples presented herein are merely illustrative of selected implementations in accordance with all possible combinations of examples. Accordingly, it is applicants' intention that the appended claims are not to be limited by the choice of examples illustrating features of the invention. Where numerical ranges are used in the claims, also included are sub-ranges within them, and variations in these ranges are also to be construed as being covered by the appended claims where possible.

Claims (1)

1. A naphthalene water reducing agent is characterized in that the raw materials comprise, by weight, 10 parts of naphthalene sulfonate, 60 parts of naphthalene oil, 84 parts of sulfonating agent, 100 parts of formaldehyde and 30 parts of water,
wherein the weight ratio of the naphthalene sulfonate is 1:2, 3-dihydroxy naphthalene-6-sodium sulfonate and 4-amino-5-hydroxy naphthalene-2, 7-sodium disulfonate,
the sulfonating agent is prepared from the following components in percentage by weight: 0.4:0.5 of a mixture of 98% by weight of concentrated sulfuric acid, sodium metabisulfite and sodium sulfite,
the preparation method of the naphthalene water reducer comprises the following steps: adding naphthalene sulfonate and naphthalene oil into a reaction vessel, heating to 150 ℃, then dropwise adding a sulfonating agent, keeping the temperature for 2.5h after dropwise adding within 30min, then cooling to 120 ℃, adding water, and keeping the temperature for 0.2h; then dripping formaldehyde, and keeping the temperature for 2 hours; then cooling to below 80 ℃, adding 32wt% of sodium hydroxide solution to neutralize to a pH value of 7-9, and obtaining the naphthalene water reducer.
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CN112830702B (en) * 2021-01-21 2022-06-21 福州宏通建材有限公司 High slump loss resistant additive suitable for concrete and preparation process thereof
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CN106117482A (en) * 2016-06-29 2016-11-16 南京瑞迪高新技术有限公司 A kind of modified high-thin arch dam naphthalene water reducer and preparation method thereof

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CN103172293A (en) * 2013-03-25 2013-06-26 萧县鑫固混凝土外加剂有限公司 Technical formula and production technology for preparing naphthalene-based superplasticizer
CN105801786A (en) * 2016-03-10 2016-07-27 安徽鑫固环保股份有限公司 Low-cost modified naphthalene-based superplasticizer with high slump-keeping property and preparation method thereof
CN106117482A (en) * 2016-06-29 2016-11-16 南京瑞迪高新技术有限公司 A kind of modified high-thin arch dam naphthalene water reducer and preparation method thereof

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