CN112831001B

CN112831001B - Anti-mud composite polycarboxylate superplasticizer and preparation method thereof

Info

Publication number: CN112831001B
Application number: CN202110035011.3A
Authority: CN
Inventors: 杨海华
Original assignee: Jiangsu Xingzhu Hongye New Material Co ltd
Current assignee: Jiangsu Xingzhu Hongye New Material Co ltd
Priority date: 2021-01-12
Filing date: 2021-01-12
Publication date: 2022-10-04
Anticipated expiration: 2041-01-12
Also published as: CN112831001A

Abstract

The invention belongs to the technical field of water reducing agents, and particularly relates to a mud-resistant composite polycarboxylic acid water reducing agent and a preparation method thereof. The mud-resistant composite polycarboxylate superplasticizer is prepared from raw materials including a polyether macromonomer, a functional monomer, a chain transfer agent, an oxidant, a reducing agent and a neutralizer. The water reducing agent prepared by the method can achieve excellent anti-mud effect, short slump loss resistant time, extremely high raw material utilization rate and cost reduction when the doping amount is 0.2-0.6% of the weight of the mud; on the other hand, the scheme in the application is obtained by researching a large number of creative experiments, and the polyether macromonomer with a special hydroxyl value plays different roles, so that the water reducing rate of the soil is greatly improved, and the compressive strength of the soil is also improved.

Description

Anti-mud composite polycarboxylate superplasticizer and preparation method thereof

Technical Field

The invention belongs to the technical field of water reducing agents, and particularly relates to a mud-resistant composite polycarboxylic acid water reducing agent and a preparation method thereof.

Background

A polycarboxylic acid water reducing agent (Polycarboxylate Superplasticizer) is a high-performance water reducing agent and is a cement dispersing agent in cement concrete application. It is green, environment friendly, non-flammable and non-explosive. The method is widely applied to projects such as highways, tunnels, high-rise buildings and the like.

The polycarboxylic acid high-performance water reducing agent really designs an effective molecular structure according to the action mechanism of the dispersed cement, has a super-dispersion type, can prevent the slump loss of concrete without causing obvious slow setting, exerts a higher plasticizing effect under low dosage, has good fluidity retention, large freedom degree on cement adaptation to wide molecular structure, multiple synthesis technologies, large scope of high performance, has obvious concrete reinforcing effect, can reduce concrete shrinkage, has the technical performance characteristics of extremely low content of harmful substances and the like, gives excellent construction workability, good strength development and excellent durability to the concrete, has good comprehensive technical performance advantages and environmental protection characteristics, and meets the requirements of modern concrete engineering.

Chinese patent with application number CN110759663A discloses a preparation method and application of an anti-mud polycarboxylic acid water reducing agent, and the method disclosed in the patent obtains the water reducing agent with simple synthesis process by free radical polymerization of unsaturated polyether macromonomer and unsaturated small monomer. However, the unsaturated polyether macromonomer used in the patent publication has a large molecular weight, and the amount of the water reducing agent prepared by using the monomer having an excessively large molecular weight for the polycarboxylic acid water reducing agent may need to be controlled to achieve a good effect. Therefore, in view of the current situation, a water reducing agent with a low content and high efficiency is an important research content of researchers.

Disclosure of Invention

In order to solve the technical problems, the invention provides an anti-mud composite polycarboxylic acid water reducing agent in a first aspect.

As a preferred technical scheme, the preparation raw materials also comprise ethylene diamine tetraacetic acid, a silane coupling agent and deionized water.

As a preferable technical solution, the polyether macromonomer is selected from at least one of prenol polyoxyethylene ether, polytetrahydrofuran ether glycol, lauryl alcohol polyoxyethylene ether, and methallyl polyoxyethylene ether.

As a preferable technical scheme, the hydroxyl value of the polyether macromonomer is 15-30mgKOH/g.

As a preferable technical scheme, the hydroxyl value of the polyether macromonomer is 21-26mgKOH/g.

As a preferable technical scheme, the functional monomer is selected from one or more of 2-acrylamide-2-methyl propylene sulfonic acid, sodium methallyl sulfonate, acrylamide and maleic anhydride.

As a preferable technical scheme, the chain transfer agent is selected from one or more of mercaptopropionic acid, mercaptoacetic acid and sodium hypophosphite.

As a preferable technical scheme, the reducing agent is selected from one or more of ascorbic acid, sodium formaldehyde sulfoxylate, ferrous sulfate and sodium bisulfite.

As a preferred technical scheme, the preparation raw materials comprise the following components in parts by weight: 300-400 parts of polyether macromonomer, 19-30 parts of functional monomer, 0.9-1.5 parts of chain transfer agent, 3-5 parts of oxidant, 0.8-2 parts of reducing agent, 2-10 parts of neutralizer, 1-4 parts of ethylene diamine tetraacetic acid, 3-10 parts of silane coupling agent and 300-500 parts of deionized water.

The invention provides a preparation method of an anti-mud composite polycarboxylate superplasticizer, which comprises the following steps:

s1: dissolving polyether macromonomer and functional monomer in deionized water, then adding ethylenediamine tetraacetic acid, a chain transfer agent and a silane coupling agent, and stirring to obtain a mixed solution;

s2: adding an oxidant into the step S1 for mixing;

s3: and (3) adding a reducing agent into the step S2, then adding a neutralizing agent, and adjusting the pH value of the solution to be neutral to obtain the catalyst.

Has the beneficial effects that: the water reducing agent prepared by the method can achieve excellent anti-mud effect, short slump retaining time, extremely high raw material utilization rate and reduced cost when the mixing amount is 0.2-0.6% of the weight of the mud; on the other hand, the scheme in the application is obtained by researching a large number of creative experiments, and the polyether macromonomer with a special hydroxyl value plays different roles, so that the water reducing rate of the soil is greatly improved, and the compressive strength of the soil is also improved.

Detailed Description

The present invention will be more readily understood 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.

As used herein, the term "prepared from" \8230a "is synonymous with" comprising ". As used herein, the terms "comprises," "comprising," "includes," "including," "has," "having," "contains" or any other variation thereof, are intended to cover a non-exclusive inclusion. For example, a composition, process, 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, process, method, article, or apparatus.

The conjunction "consisting of 8230comprises" excludes any non-specified elements, steps or components. If used in a claim, the phrase is intended to claim as closed, meaning that it does not contain materials other than those described, except for the conventional impurities associated therewith. When the phrase "consisting of 8230title" appears in a clause of the subject matter of the claims and not immediately after the subject matter, it defines only the elements described in the clause; other elements are not excluded from the claims as a whole.

When an amount, concentration, or other value or parameter is expressed as a range, preferred range, or as a range 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 interpreted to include 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 specified, the range is intended to include the endpoints thereof, and all integers and fractions within the range.

The singular forms "a," "an," and "the" include plural referents unless the context clearly dictates otherwise. "optional" or "either" means that the subsequently described event or events may or may not occur, and that the description includes instances where the event occurs and instances where it does not.

Approximating language, as used herein throughout the specification and claims, is intended to modify a quantity, such that the invention is not limited to the specific quantity, but includes portions that are literally received for modification without substantial change in the basic function to which the invention is related. Accordingly, the use of "about" to modify a numerical value means that the invention is not limited to the precise numerical value. In some instances, the approximating language may correspond to the precision of an instrument for measuring the value. In the present description and claims, range limitations may be combined and/or interchanged, including all sub-ranges contained therein if not otherwise stated.

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 problems, the invention provides an anti-mud composite polycarboxylate superplasticizer in a first aspect.

In some preferred embodiments, the preparation raw materials further comprise ethylene diamine tetraacetic acid, a silane coupling agent, and deionized water.

In some preferred embodiments, the polyether macromonomer is selected from at least one of prenyl polyoxyethylene ether, polytetrahydrofuran ether glycol, lauryl polyoxyethylene ether, and methallyl polyoxyethylene ether.

In some preferred embodiments, the polyether macromonomer is selected from the group consisting of prenyl polyoxyethylene ethers.

Isopentenol polyoxyethylene ether is purchased from Heian petrochemical plants in Jiangsu province.

In some preferred embodiments, the polyether macromonomer has a hydroxyl number of 15 to 30mgKOH/g.

In some preferred embodiments, the polyether macromonomer has a hydroxyl number of from 21 to 26mgKOH/g.

In some preferred embodiments, the functional monomer is selected from one or more of 2-acrylamido-2-methylpropanesulfonic acid, sodium methallylsulfonate, acrylamide, and maleic anhydride.

In some preferred embodiments, the functional monomer is selected from 2-acrylamido-2-methylpropanesulfonic acid (CAS: 15214-89-8).

In some preferred embodiments, the chain transfer agent is selected from one or more of mercaptopropionic acid, thioglycolic acid, and sodium hypophosphite.

In some preferred embodiments, the chain transfer agent is selected from the group consisting of mercaptopropionic acid and mercaptoacetic acid.

In some preferred embodiments, the weight ratio of mercaptopropionic acid to mercaptoacetic acid is 2:0.4-1.2.

In some preferred embodiments, the reducing agent is selected from one or more of ascorbic acid, sodium formaldehyde sulfoxylate, ferrous sulfate, and sodium bisulfite.

In some preferred embodiments, the reducing agent is selected from the group consisting of sodium formaldehyde sulfoxylate and sodium bisulfite.

In some preferred embodiments, the weight ratio of the sodium formaldehyde sulfoxylate to the sodium bisulfite is from 0.1 to 0.5:2.

hanging white block

The rongalite is prepared by reducing formalin in combination with sodium bisulfite, and has chemical formula of CH ₂ (OH)SO ₂ Na in the form of white block or crystalline powder, and has no smell or slight smell of Chinese chives; is easily soluble in water and slightly soluble in alcohol. It is stable at normal temperature, has strong reducibility at high temperature, and has bleaching effect.

In some preferred embodiments, the preparation raw materials comprise, by weight: 300-400 parts of polyether macromonomer, 19-30 parts of functional monomer, 0.9-1.5 parts of chain transfer agent, 3-5 parts of oxidant, 0.8-2 parts of reducing agent, 2-10 parts of neutralizer, 1-4 parts of ethylene diamine tetraacetic acid, 3-10 parts of silane coupling agent and 300-500 parts of deionized water.

In some preferred embodiments, the silane coupling agent is selected from the group consisting of aminopropyltriethoxysilane and vinyltriethoxysilane.

In some preferred embodiments, the weight ratio of aminopropyltriethoxysilane to vinyltriethoxysilane is from 2-3:1.

in the application, the applicant is obtained by a large number of creative experiments, and the flexibility of a high molecular chain section formed by a system and the dispersibility of the water reducing agent in the using process are ensured by selecting the polyether macromonomer with the hydroxyl value of 21-26mgKOH/g. In addition, the silane coupling agent, the 2-acrylamide-2-methacrylic sulfonic acid and other reactants in the application not only contain active groups capable of being adsorbed to the surfaces of cement particles, but also provide the electrostatic repulsion effect of the dispersion of soil particles, improve the dispersion performance of the water reducing agent in soil and improve the water reducing rate.

In addition, the applicant finds that the reactants can be associated with hydrogen bonds among water molecules in the soil to form a stable water film, so that particles in the soil are prevented from being in direct contact with the particles, and the condition that the using effect of the water reducing agent is reduced due to a flocculation phenomenon possibly generated by the soil is avoided.

In addition, in the experimental process, the applicant finds that when the hydroxyl value of the selected polyether macromonomer is less than 15mgKOH/g, the adsorption performance of water reducing agent molecules on the surface of soil particles is influenced, and flocculation phenomenon occurs, and the applicant speculates that the flexibility of molecular chain segments is influenced; when the hydroxyl value of the selected polyether macromonomer is greater than 30mgKOH/g, poor dispersing performance of the water reducing agent in soil is caused, and the applicant speculates that the action force between the water reducing agent and soil particles is changed possibly because of the fact that the electronegative groups in the system are less, and the dispersing performance is further influenced.

In some preferred embodiments, the oxidizing agent is selected from one or more of hydrogen peroxide, ammonium persulfate, and sodium persulfate.

In some preferred embodiments, the neutralizing agent is selected from one or more of sodium hydroxide solution, potassium hydroxide solution, triisopropanolamine, and the like.

In some preferred embodiments, the neutralizing agent is selected from triisopropanolamine.

The second aspect of the invention provides a preparation method of a mud-resistant composite polycarboxylate superplasticizer, which comprises the following steps:

s1: dissolving polyether macromonomer and functional monomer in deionized water, adding ethylene diamine tetraacetic acid, chain transfer agent and silane coupling agent, and stirring to obtain a mixed solution;

s2: adding an oxidant into the step S1 for mixing;

The present invention will be specifically described below by way of examples. It is to be noted that the following examples are given solely for the purpose of illustration and are not to be construed as limitations on the scope of the invention, as many insubstantial modifications and variations of the invention described above will now occur to those skilled in the art.

In addition, the starting materials used are all commercially available, unless otherwise specified.

Examples

Example 1

The mud-resistant composite polycarboxylate superplasticizer comprises the following preparation raw materials in parts by weight: 300 parts of prenyl polyoxyethylene ether, 19 parts of 2-acrylamide-2-methylpropanesulfonic acid, 0.9 part of chain transfer agent, 3 parts of ammonium persulfate, 0.8 part of reducing agent, 2 parts of triisopropanolamine, 1 part of ethylene diamine tetraacetic acid, 3 parts of silane coupling agent and 300 parts of deionized water.

The hydroxyl value of the prenyl polyoxyethylene ether is 21-26mgKOH/g, and the prenyl polyoxyethylene ether is purchased from Heian petrochemical plants in Jiangsu province.

The chain transfer agent is selected from mercaptopropionic acid and mercaptoacetic acid, and the weight ratio of the chain transfer agent to the mercaptoacetic acid is 2:0.7.

the reducing agent is selected from sodium formaldehyde sulfoxylate and sodium bisulfite, and the weight ratio of the reducing agent to the sodium formaldehyde sulfoxylate is 0.3:2.

the silane coupling agent is selected from aminopropyltriethoxysilane and vinyl triethoxysilane, and the weight ratio of the silane coupling agent is 2.4:1.

2-acrylamido-2-methylpropanesulfonic acid (CAS: 15214-89-8).

A preparation method of a mud-resistant composite polycarboxylate superplasticizer comprises the following steps:

s1: dissolving prenyl polyoxyethylene ether and 2-acrylamide-2-methylpropanesulfonic acid in deionized water, adding ethylene diamine tetraacetic acid, a chain transfer agent and a silane coupling agent, and stirring to obtain a mixed solution;

s2: adding ammonium persulfate into the step S1 and mixing;

s3: and (3) adding a reducing agent in the step S2, then adding triisopropanolamine, and adjusting the pH of the solution to be neutral to obtain the copper-zinc alloy.

Example 2

The mud-resistant composite polycarboxylate superplasticizer comprises the following preparation raw materials in parts by weight: 400 parts of prenyl alcohol polyoxyethylene ether, 30 parts of 2-acrylamide-2-methyl propylene sulfonic acid, 1.5 parts of a chain transfer agent, 5 parts of ammonium persulfate, 2 parts of a reducing agent, 10 parts of triisopropanolamine, 4 parts of ethylene diamine tetraacetic acid, 10 parts of a silane coupling agent and 400 parts of deionized water.

2-acrylamido-2-methylpropanesulfonic acid (CAS: 15214-89-8).

A preparation method of a mud-resistant composite polycarboxylate superplasticizer, which refers to example 1.

Example 3

The mud-resistant composite polycarboxylate superplasticizer comprises the following preparation raw materials in parts by weight: 350 parts of prenyl alcohol polyoxyethylene ether, 25 parts of 2-acrylamide-2-methylpropanesulfonic acid, 1.2 parts of a chain transfer agent, 4 parts of ammonium persulfate, 1.5 parts of a reducing agent, 6 parts of triisopropanolamine, 2 parts of ethylene diamine tetraacetic acid, 5 parts of a silane coupling agent and 300 parts of deionized water.

The hydroxyl value of the isoamylene alcohol polyoxyethylene ether is 21-26mgKOH/g, and the isoamylene alcohol polyoxyethylene ether is purchased from the Heian petrochemical plant in Jiangsu province.

2-acrylamido-2-methylpropanesulfonic acid (CAS: 15214-89-8).

A preparation method of a mud-resistant composite polycarboxylate superplasticizer, which is shown in the following example 1.

Example 4

The concrete implementation manner of the mud-resistant composite polycarboxylate water reducer is the same as that in example 3, and the concrete difference of the mud-resistant composite polycarboxylate water reducer from example 3 is that the hydroxyl value of the prenol polyoxyethylene ether is 65-75mgKOH/g, which is purchased from Chachentai blue sky fine chemical industry Co.

Example 5

The concrete implementation mode of the mud-resistant composite polycarboxylate superplasticizer is the same as that in example 3, and the difference from the example 3 is that potassium hydroxide is selected as a neutralizer.

Example 6

The concrete implementation mode of the mud-resistant composite polycarboxylate superplasticizer is the same as that in example 3, and the difference from the example 3 is that the weight ratio of aminopropyltriethoxysilane to vinyltriethoxysilane is 1:1.

example 7

The concrete implementation mode of the mud-resistant composite polycarboxylate water reducer is the same as that of example 3, and the difference of the concrete implementation mode of the mud-resistant composite polycarboxylate water reducer from example 3 is that a silane coupling agent is selected from aminopropyltriethoxysilane.

Example 8

The concrete implementation mode of the mud-resistant composite polycarboxylate superplasticizer is the same as that of example 3, and the difference of the concrete implementation mode of the mud-resistant composite polycarboxylate superplasticizer from example 3 is that a silane coupling agent is selected from vinyl tri (2-methoxyethoxy) silane.

And (4) performance testing:

the water reducing agents prepared in examples 1 to 8 were used for water reduction rate and compressive strength tests;

1. and (3) testing the water reducing rate: the mixing amount of the water reducing agent is 0.3% of the weight of the soil, the water reducing rate is calculated by the reduction of the water content in the soil before and after the test, the water reducing rate = the content of the soil after the water reducing agent is added/the content of the soil before the water reducing agent is added x 100%, and the results are counted in the following table.

2. And (3) testing the compression resistance: the test standard was referred to GB/T50080-2016 and the test results were tabulated below.

Experiment of the invention	Water reduction rate/%)	7 day compressive strength/MPa	28 day compressive strength/MPa
				Example 1	37.8	65.8	63.5
Example 2	38.6	67.2	66.9
				Example 3	39.7	69.6	69.3
Example 4	18.6	38.2	25.3
				Example 5	30.3	56.9	52.6
Example 6	28.5	46.5	40.7
				Example 7	31.2	47.3	43.6
Example 8	26.7	42.3	38.2

The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present invention. It should be noted that various changes and modifications can be made by those skilled in the art without departing from the spirit of the invention, and these changes and modifications are all within the scope of the invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.

Claims

1. The mud-resistant composite polycarboxylate superplasticizer is characterized in that the preparation raw materials comprise a polyether macromonomer, a functional monomer, a chain transfer agent, an oxidant, a reducing agent and a neutralizer; the preparation raw materials comprise the following components in parts by weight: 300-400 parts of polyether macromonomer, 19-30 parts of functional monomer, 0.9-1.5 parts of chain transfer agent, 3-5 parts of oxidant, 0.8-2 parts of reducing agent, 2-10 parts of neutralizer, 1-4 parts of ethylene diamine tetraacetic acid, 3-10 parts of silane coupling agent and 300-500 parts of deionized water; the neutralizing agent is selected from triisopropanolamine; the polyether macromonomer is selected from prenyl polyoxyethylene ether, the hydroxyl value of the prenyl polyoxyethylene ether is 21-26mgKOH/g, the functional monomer is selected from 2-acrylamide-2-methacrylic sulfonic acid, the silane coupling agent is selected from aminopropyl triethoxysilane and vinyl triethoxysilane, and the weight ratio of the silane coupling agent is 2.4:1.

2. the mud-resistant composite polycarboxylic acid water reducing agent according to claim 1, wherein the chain transfer agent is one or more selected from mercaptopropionic acid, thioglycolic acid and sodium hypophosphite.

3. The mud-resistant composite polycarboxylic acid water reducing agent according to claim 1, characterized in that the reducing agent is selected from one or more of ascorbic acid, sodium formaldehyde sulfoxylate, ferrous sulfate and sodium bisulfite.

4. The preparation method of the mud-resistant composite polycarboxylate superplasticizer according to any one of claims 2 to 3, characterized by comprising the following steps:

s1: dissolving a polyether macromonomer and a functional monomer in deionized water, adding ethylene diamine tetraacetic acid, a chain transfer agent and a silane coupling agent, and stirring to obtain a mixed solution;

s2: adding an oxidant into the step S1 for mixing;