CN1693263A

CN1693263A - Concrete water-reducing agent and its production method

Info

Publication number: CN1693263A
Application number: CN 200510034012
Authority: CN
Inventors: 彭延山
Original assignee: YUEHE INIDUSTRIAL CO Ltd GUANGDONG
Current assignee: YUEHE INIDUSTRIAL CO Ltd GUANGDONG
Priority date: 2005-04-11
Filing date: 2005-04-11
Publication date: 2005-11-09

Abstract

A water reducing agent for concrete is proportionally prepared from industrial nephthalene, washing oil as the by-product of coking, sulfuric acid, formaldehyde, modifier and liquid alkali through fusing, sulfonating, hydrolyzing, modifying, condensating and neutralizing with alkali.

Description

Concrete water reducing agent and production method thereof

Technical Field

The invention relates to the field of building materials, in particular to a chemical admixture technology for improving concrete performance, which comprises the following steps: a concrete water reducing agent and a production method thereof. The concrete water reducing agent is mainly applied to improving the functions of concrete.

Background

As a novel material, namely an additive, the concrete high-efficiency water reducing agent not only can improve the technical level of construction and the performance of concrete, but also can save a large amount of cement, manpower and material resources, and has extremely high value, which is proved by the fact.

However, the raw materials required for producing the concrete high-efficiency water reducing agent in the prior art are all short-cut chemical raw materials, such as industrial naphthalene, acetone, phenol and the like. This causes problems of shortage of raw materials and high production cost. Meanwhile, a large amount of by-products, namely industrial waste residues and waste liquid, are generated in the domestic coking and petrochemical industries, so that the environmental pollution is caused. Fortunately, industrial waste residues and waste liquids also contain some byproducts which can be produced and utilized, such as: washing oil from coking by-product. Can wash oil be used to replace industrial naphthalene in the production of high-efficiency water reducing agent? A great deal of research is carried out on the washing oil products by various additive manufacturers, and the conclusion is that the following serious defects exist: the air entraining amount is too large, the slump loss is fast, the later strength is low, and the road is obstructed. It is known that, at present, no method exists except that Switzerland (Dalian) Cika (SIKA) can replace 37.5 percent of industrial naphthalene by about 30 percent of methylnaphthalene extracted from wash oil, and the performance requirements of the market on the concrete high-efficiency water reducing agent serving as an additive cannot be met.

Disclosure of Invention

The invention aims to provide a novel high-efficiency concrete water reducing agent which can greatly replace industrial naphthalene by using a coking byproduct washing oil, thereby improving and improving the performance of concrete and prolonging the service life of the concrete.

The second purpose of the invention is to provide a method for producing the water reducing agent.

The technical scheme of the invention is as follows:

the concrete water reducing agent is characterized by comprising the following raw materials in parts by weight:

industrial naphthalene and washing oil are 1: 0.20-0.55;

(industrial naphthalene + washing oil), sulfuric acid, formaldehyde, modifier and liquid alkali

＝1∶1～1.1∶0.56～0.93∶0.01～0.03∶0.94～1.70。

The production method of the water reducing agent comprises the following steps:

a. melting: adding washing oil and industrial naphthalene in a reaction tank according to a ratio, and heating to 120-130 ℃ for melting;

b. sulfonation: adding concentrated sulfuric acid to sulfonate the mixture, controlling the temperature to be 150-160 ℃, and preserving the temperature for 2-4 hours to generate aromatic ring sulfonic acid derivatives;

c. hydrolysis: adding cold water for hydrolysis at the temperature of 80 ℃ to remove the 2-aromatic ring sulfonic acid;

d. modification: adding a modifier so as to form carboxyl during condensation and carry out lateral grafting modification to inhibit air entrainment of methyl and other groups, and simultaneously adjusting the acidity to be 30%;

e. condensation: adding formaldehyde at 75 ℃ for condensation to generate a linear molecular chain, so as to increase the surface activity, wherein the condensation temperature is controlled to be 90-100 ℃, and the time is controlled to be 3-5 hours;

f. alkali neutralization: and adding liquid alkali to neutralize the condensate alkali, and adjusting the pH value to be slightly alkaline so as to obtain a liquid water reducing agent product.

The advantages of the invention are used.

Experiments prove that: the concrete water reducing agent prepared by the method has the advantages that the proportion of coking byproduct washing oil which can replace industrial naphthalene reaches 45 percent, the price of the product can be greatly reduced while the environmental protection is promoted, and the condensation performance of the product is basically unchanged.

Contrary to traditional producers, it is only with industry naphthalene and wash oil or methylnaphthalene mix condensation, because the bleed air of methyl can make the bleed air nature of product improve by a wide margin to introduce more than 5% bubble in the concrete, so just reduced the performance of concrete, made this product be difficult to normal use. The invention fully considers the problem of air entraining property of methyl, utilizes the HLB hydrophilic-lipophilic balance theory, and adds the modifier to adjust the HLB value of the product, thereby achieving the effect of inhibiting the air entraining of the methyl. The invention used as the additive for concrete buildings has the advantages of high strength, good performance, capability of reducing the peak value of cement hydration heat, improvement of concrete uniformity, prolonging of concrete service life and the like.

The invention is further described below in conjunction with specific formulations.

Detailed Description

Concrete water reducing agent:

example 1: the concrete water reducing agent comprises the following raw materials in parts by weight:

industrial naphthalene and washing oil are 1: 0.20;

＝1∶1∶0.56∶0.01∶0.94。

Example 2:

industrial naphthalene and washing oil are 1: 0.40;

＝1∶1～11∶0.7∶0.02∶1

Example 3:

industrial naphthalene and washing oil are 1: 0.55;

＝1∶1.1∶0.93∶3∶1.70。

d. modification: adding modifier to form carboxyl group for side grafting modification to inhibit air entraining of methyl group and other groups while regulating acidity to 30%.

The action principle of the modifier is as follows: the modifier is a carboxylic ester material which, after hydrolysis, will undergo an electrophilic substitution reaction with the H of the sulfonic acid group to produce-SO₃H₂Grafting functional groups of COOR type. The choice of R depends on the final HLB value of the entire linear molecular chain.

Relationship between HLB value and Performance

HLB value of 1-3: defoaming action

HLB value is 3-6: emulsion Dispersion (Water-in-oil type)

HLB value is 7-18: emulsification Dispersion (oil-in-water type)

HLB value 12-15: wetting action

HLB value is 13-15: decontamination effect

HLB value 15-18: solubilization

Note: the HLB value (Hydrophile-Liphile Balance), the most successful approach is probably the method proposed by Griffin (Griffin), i.e. the hydrophilic-lipophilic Balance.

The sulfonation in step b is carried out by substituting a hydrogen atom on the aromatic nucleus to form a sulfonic acid compound (ArSO)₃H, Ar is benzene ring), typical reaction formulas are (I formula and II formula):

the hydrolysis and modification of the steps c and d have the function of eliminating α -naphthalenesulfonic acid in the reaction so as to be beneficial to the smooth proceeding of the condensation reaction, and the typical reaction formula is (III):

wherein M is a modified functional group, typically a derivative of-COOR;

step e condensation is the formation of a polymer via a condensation reaction, typically of the formulae (IV, V):

CH₂O+H⁺→CH₂OH⁺

(IV)

and f, neutralizing the alkali by NaOH to generate a final product concrete water reducer, namely polysulfonate, and converting redundant acid into sulfate, wherein the typical reaction formula is (VI):

Claims

1. the concrete water reducing agent is characterized by comprising the following raw materials in parts by weight:

industrial naphthalene and washing oil are 1: 0.20-0.55;

＝1∶1～1.1∶0.56～0.93∶0.01～0.03∶0.94～1.70。

2. The production method of the concrete water reducer of claim 1 is characterized by comprising the following production process steps:

3. The method according to claim 2, wherein the sulfonation in step b is carried out by substituting a hydrogen atom of the aromatic nucleus with a sulfonic acid compound (ArSO)₃H) Typical reaction formulas are (I formula and II formula):

4. the method according to claim 2, wherein the hydrolysis and modification of steps c and d are carried out to eliminate α -naphthalene sulfonic acid in the reaction to facilitate the condensation reaction, and the reaction formula is typically (III):

wherein M is a modifying functional group, typically a derivative of-COOR.

5. The method according to claim 2, characterized in that the step e-condensation is a process of forming a polymer via a condensation reaction, typically of the formula (IV, V):

(IV)

6. the method of claim 2, wherein the alkali neutralization ofstep f is performed with NaOH to produce a final product concrete water reducer, a polysulfonate, and excess acid is converted to sulfate, typically of the formula (VI):