阅读说明：本技术 一种降粘型聚羧酸减水剂及其制备方法 (Viscosity-reducing polycarboxylate superplasticizer and preparation method thereof ) 是由 刘斌 于 2020-06-04 设计创作，主要内容包括：本发明涉及混凝土外加剂技术领域,具体涉及一种降粘型聚羧酸减水剂及其制备方法,按重量份计,制备原料至少包括：聚醚8-16份、酯类化合物3-10份、磺酸盐化合物12-18份、功能单体20-40份、引发剂0.5-3份、pH调节剂1-5份、水60-80份。(The invention relates to the technical field of concrete admixtures, in particular to a viscosity-reducing polycarboxylic acid water reducer and a preparation method thereof, wherein the preparation raw materials at least comprise the following components in parts by weight: 8-16 parts of polyether, 3-10 parts of ester compound, 12-18 parts of sulfonate compound, 20-40 parts of functional monomer, 0.5-3 parts of initiator, 1-5 parts of pH regulator and 60-80 parts of water.)

1. The viscosity reduction type polycarboxylate superplasticizer is characterized by comprising the following preparation raw materials in parts by weight: 8-16 parts of polyether, 3-10 parts of ester compound, 12-18 parts of sulfonate compound, 20-40 parts of functional monomer, 0.5-3 parts of initiator, 1-5 parts of pH regulator and 60-80 parts of water.

2. The viscosity-reducing polycarboxylate water reducer according to claim 1, wherein the polyoxyethylene enol ether is isopentenol polyoxyethylene ether.

3. The viscosity-reducing polycarboxylate superplasticizer according to claim 2, wherein the molecular weight of said prenyl polyoxyethylene ether is 1800-3000.

4. The viscosity-reducing polycarboxylic acid water reducing agent according to claim 1, wherein the ester compound is selected from one or more of vinyl acetate, allyl acetate, diethylhexyl maleate, diethyl maleate, polyethylene glycol mono maleate, dilauryl maleate, and diethylene glycol maleate.

5. The viscosity-reduction type polycarboxylate superplasticizer according to claim 1 or 4, wherein the ester compound is a combination of vinyl acetate and diethyl maleate, wherein the mass ratio of vinyl acetate to diethyl maleate is 1: (0.6-3.25).

6. The viscosity-reducing polycarboxylic acid water reducer according to claim 1, characterized in that the sulfonate compound contains at least one allyl group.

7. The viscosity-reducing polycarboxylate water reducer according to claim 1, wherein the functional monomer is one or more selected from acrylic acid, methacrylic acid, acrylic ester, methacrylic ester, hydroxybutyl methacrylate, hydroxyethyl methacrylate, acrylamide, hydroxymethyl acrylamide, diacetone acrylamide, ethyl acetoacetate methacrylate, glycidyl methacrylate, dimethylaminoethyl methacrylate, hydroxypropyl acrylate and hydroxyethyl acrylate.

8. The viscosity-reducing polycarboxylic acid water reducing agent according to claim 1, wherein the initiator is selected from one or more of benzoyl peroxide, lauroyl peroxide, dicumyl peroxide, azobisisobutyronitrile, azobisisoheptonitrile, N-dimethylaniline, potassium sulfate, ammonium persulfate and sodium sulfite.

9. The viscosity-reducing polycarboxylic acid water reducing agent according to claim 1, wherein the pH regulator is selected from one or more of sodium bicarbonate, potassium bicarbonate, sodium hydroxide, potassium hydroxide, sodium carbonate and potassium carbonate.

10. The preparation method of the viscosity-reducing polycarboxylate superplasticizer according to any one of claims 1 to 9, wherein the preparation method at least comprises the following steps:

(1) adding polyether into a container, uniformly stirring, dropwise adding a mixture of an ester compound, a sulfonate compound, a functional monomer and an initiator, and controlling the dropwise adding time to be 3-3.5 h;

(2) after the dropwise addition is finished, preserving the heat for 0.5-1.5h, cooling to 30-45 ℃, adding a pH regulator and water, and stirring to obtain the product.

Technical Field

The invention relates to the technical field of concrete admixtures, in particular to a viscosity-reducing polycarboxylic acid water reducer and a preparation method thereof.

Background

The polycarboxylic acid water reducing agent has the advantages of low mixing amount, high water reducing rate, strong designability, environmental friendliness and the like, and becomes a concrete admixture which is most widely applied. High-rise and super high-rise buildings require that concrete must reach a certain strength grade, pumping construction of the high-rise building concrete has high requirements on the workability of the concrete, and in order to reach a high strength grade, the concrete can be generally realized by methods of reducing water-cement ratio, increasing the using amount of a cementing material, increasing the proportion of a mineral admixture and the like, but the measures can also cause the problems of increasing the viscosity, reducing the fluidity and the like of the concrete.

Disclosure of Invention

In order to solve the technical problems, the first aspect of the invention provides a viscosity-reducing polycarboxylic acid water reducer, which comprises the following raw materials in parts by weight: 8-16 parts of polyether, 3-10 parts of ester compound, 12-18 parts of sulfonate compound, 20-40 parts of functional monomer, 0.5-3 parts of initiator, 1-5 parts of pH regulator and 60-80 parts of water.

As a preferable technical scheme of the invention, the enol polyoxyethylene ether is isopentenol polyoxyethylene ether.

As a preferable technical scheme of the invention, the molecular weight of the prenol polyoxyethylene ether is 1800-3000.

As a preferred embodiment of the present invention, the ester compound is selected from one or more of vinyl acetate, allyl acetate, diethylhexyl maleate, diethyl maleate, polyethylene glycol mono maleate, dilauryl maleate, and diethylene glycol maleate.

As a preferred technical solution of the present invention, the ester compound is a combination of vinyl acetate and diethyl maleate, wherein the mass ratio of vinyl acetate to diethyl maleate is 1: (0.6-3.25).

In a preferred embodiment of the present invention, the sulfonate compound contains at least one allyl group.

In a preferred embodiment of the present invention, the functional monomer is selected from one or more of acrylic acid, methacrylic acid, acrylate, methacrylate, hydroxybutyl methacrylate, hydroxyethyl methacrylate, acrylamide, methylolacrylamide, diacetone acrylamide, ethyl acetoacetate methacrylate, glycidyl methacrylate, dimethylaminoethyl methacrylate, hydroxypropyl acrylate, and hydroxyethyl acrylate.

In a preferred embodiment of the present invention, the initiator is selected from one or more of benzoyl peroxide, lauroyl peroxide, dicumyl peroxide, azobisisobutyronitrile, azobisisoheptonitrile, N-dimethylaniline, potassium sulfate, ammonium persulfate, and sodium sulfite.

In a preferred embodiment of the present invention, the pH adjuster is one or more selected from sodium bicarbonate, potassium bicarbonate, sodium hydroxide, potassium hydroxide, sodium carbonate, and potassium carbonate.

The second aspect of the invention provides a preparation method of a viscosity-reducing polycarboxylate superplasticizer, which at least comprises the following steps:

(1) adding polyether into a container, uniformly stirring, dropwise adding a mixture of an ester compound, a sulfonate compound, a functional monomer and an initiator, and controlling the dropwise adding time to be 3-3.5 h;

(2) after the dropwise addition is finished, preserving the heat for 0.5-1.5h, cooling to 30-45 ℃, adding a pH regulator and water, and stirring to obtain the product.

Has the advantages that: the invention provides a viscosity-reduction type polycarboxylate water reducer and a preparation method thereof, wherein polyether, ester compounds, sulfonate compounds, functional monomers, initiators and pH regulators are adopted, the proportion among the components is reasonably regulated, and monomers with specific structures and polymers with specific molecular weights are selected to obtain the polycarboxylate water reducer with the viscosity reduction effect.

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 term "prepared from …" as used herein is synonymous with "comprising". The terms "comprises," "comprising," "includes," "including," "has," "having," "contains," "containing," or any other variation thereof, as used herein, 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 …" excludes any unspecified 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 …" appears in a clause of the subject matter of the claims rather than 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 a range of "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 stated, 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 "any" 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 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 stated number clearly indicates that the singular form is intended.

In order to solve the technical problems, the first aspect of the invention provides a viscosity-reducing polycarboxylic acid water reducer, which comprises the following raw materials in parts by weight: 8-16 parts of polyether, 3-10 parts of ester compound, 12-18 parts of sulfonate compound, 20-40 parts of functional monomer, 0.5-3 parts of initiator, 1-5 parts of pH regulator and 60-80 parts of water.

In a preferred embodiment, the viscosity-reducing polycarboxylate superplasticizer provided by the invention is prepared from at least the following raw materials in parts by weight: 10-15 parts of polyether, 5-8 parts of ester compound, 14-16 parts of sulfonate compound, 23-35 parts of functional monomer, 1-2 parts of initiator, 2-4 parts of pH regulator and 65-75 parts of water.

In a most preferred embodiment, the viscosity-reducing polycarboxylate superplasticizer provided by the invention is prepared from at least the following raw materials in parts by weight: 13 parts of polyether, 7.3 parts of ester compound, 15 parts of sulfonate compound, 30 parts of functional monomer, 1.5 parts of initiator, 3.5 parts of pH regulator and 70 parts of water.

Polyether

In a preferred embodiment, the polyether of the present invention is an enol ethoxylate.

In a more preferred embodiment, the polyoxyethylene enol ether according to the present invention is a polyoxyethylene prenyl ether.

In a more preferred embodiment, the molecular weight of the prenyl polyoxyethylene ether of the present invention is 1800-3000.

In a most preferred embodiment, the prenyl polyoxyethylene ethers of the present invention have a molecular weight of 2400.

Ester compounds

The ester compound of the present invention refers to a compound containing an ester group.

In a preferred embodiment, the ester compound of the present invention is selected from one or more of vinyl acetate, allyl acetate, diethylhexyl maleate, diethyl maleate, polyethylene glycol mono maleate, dilauryl maleate, and diethylene glycol maleate.

In a more preferred embodiment, the ester compound of the present invention is a combination of vinyl acetate and diethyl maleate, wherein the mass ratio of vinyl acetate to diethyl maleate is 1: (0.6-3.25).

In a more preferred embodiment, the ester compound of the present invention is a combination of vinyl acetate and diethyl maleate, wherein the mass ratio of vinyl acetate to diethyl maleate is 1: 2.3.

the diethyl maleate is a colorless transparent liquid, can be mixed with various organic solvents, is partially dissolved in benzene and chloroform, and is dissolved in water at 30 ℃ by 1.4 percent; water was dissolved in diethyl maleate at 1.9%. Forming an azeotropic mixture with 88.2 percent of water, wherein the azeotropic point is 99.65 ℃; it can be used as intermediate of agricultural chemicals for preparing organophosphorus agricultural chemical malathion and for producing perfume.

The vinyl acetate is a different name of vinyl acetate, and other different names of the vinyl acetate and the vinyl acetate are vinyl acetate and vinyl acetate which are raw materials for preparing vinylon. Is colorless liquid and has sweet ether taste; slightly soluble in water, and soluble in alcohol, acetone, benzene, and chloroform. Vinyl acetate is flammable and its vapors can form explosive mixtures with air. When exposed fire and high heat are encountered, the combustion and explosion can be caused. Can react with oxidant strongly. Are highly susceptible to polymerization by heat, light or trace amounts of peroxide, and commercial products containing inhibitors can also polymerize violently upon contact with peroxide. Its vapor is heavier than air and can diffuse to a considerable distance at a lower position, causing a flashback in the case of an open flame. The method is mainly used for producing polyvinyl alcohol resin and synthetic fiber. The monomers can be copolymerized to produce the adhesive with various purposes; it can also be copolymerized, grafted and blocked with vinyl chloride, acrylonitrile, crotonic acid, acrylic acid and vinyl monomer to prepare high molecular synthetic materials with different properties.

Sulfonate compound

The sulfonate compound belongs to a detergent dispersant substance, and has high alkalinity and calcium content and good oil sludge cleaning effect. The sulfonate has the advantages of easily available raw materials, low price, good high-temperature detergency, strong acid neutralization capacity, good rust resistance and certain dispersing and solubilizing capacities.

In a preferred embodiment, the sulfonate compound of the present invention contains at least one allyl group.

In a more preferred embodiment, the sulfonate compound of the present invention is an allyl sulfonate.

In a most preferred embodiment, the allyl sulfonate of the present invention is sodium allyl sulfonate.

Functional monomer

The functional monomer of the present invention refers to a monomer providing a specific functional group.

In a preferred embodiment, the functional monomer of the present invention is selected from one or more of acrylic acid, methacrylic acid, acrylate, methacrylate, hydroxybutyl methacrylate, hydroxyethyl methacrylate, acrylamide, methylolacrylamide, diacetone acrylamide, acetoacetic acid ethyl methacrylate, glycidyl methacrylate, dimethylaminoethyl methacrylate, hydroxypropyl acrylate, hydroxyethyl acrylate.

In a more preferred embodiment, the functional monomer of the present invention is a combination of acrylic acid and hydroxyethyl acrylate, wherein the mass ratio of acrylic acid to hydroxyethyl acrylate is 5.25: (0.5-1.6).

In a most preferred embodiment, the functional monomer of the present invention is a combination of acrylic acid and hydroxyethyl acrylate, wherein the mass ratio of acrylic acid to hydroxyethyl acrylate is 5.25: 1.

initiator

The initiator refers to a compound which is easily decomposed into free radicals (namely primary free radicals) by heating, can be used for initiating free radical polymerization and copolymerization of vinyl and diene monomers, and can also be used for crosslinking curing and macromolecular crosslinking reaction of unsaturated polyester.

In one embodiment, the initiator is selected from one or more of benzoyl peroxide, lauroyl peroxide, dicumyl peroxide, azobisisobutyronitrile, azobisisoheptonitrile, N-dimethylaniline, potassium sulfate, ammonium persulfate, sodium sulfite.

In a most preferred embodiment, the initiator of the present invention is ammonium persulfate.

pH regulator

The pH regulator is also called as acidity regulator and is used for maintaining or changing the pH value in the system.

In a preferred embodiment, the pH regulator of the present invention is selected from one or more of sodium bicarbonate, potassium bicarbonate, sodium hydroxide, potassium hydroxide, sodium carbonate, and potassium carbonate.

In a most preferred embodiment, the pH adjusting agent of the present invention is sodium hydroxide.

The inventor finds in experiments that the ester compound and the functional monomer are selected to be compounded, particularly when the ester compound is vinyl acetate and diethyl maleate, and the functional monomer is a combination of acrylic acid and hydroxyethyl acrylate, wherein the mass ratio of the acrylic acid to the hydroxyethyl acrylate is 5.25: (0.5-1.6), the method is helpful for forming the polycarboxylic acid type water reducing agent with shorter molecular side chain, further reducing the thickness of a hydration film of the polycarboxylic acid type water reducing agent on the surface of cement particles, and releasing more free water: on the other hand, the invention also adds polyether and effectively controls the molecular weight of the polyether, so that a specific content of hydrophobic groups are introduced into the molecular structure of the polycarboxylic acid water reducing agent, the possibility of generating bound water by combining the polycarboxylic acid water reducing agent molecules with water is reduced, a certain amount of free water is released, and the fluidity is improved and the segregation resistance is improved.

The second aspect of the invention provides a preparation method of a viscosity-reducing polycarboxylate superplasticizer, which at least comprises the following steps:

(1) adding polyether into a container, uniformly stirring, dropwise adding a mixture of an ester compound, a sulfonate compound, a functional monomer and an initiator, and controlling the dropwise adding time to be 3-3.5 h;

(2) after the dropwise addition is finished, preserving the heat for 0.5-1.5h, cooling to 30-45 ℃, adding a pH regulator and water, and stirring to obtain the product.

It should be noted that the following examples are only for illustrating the present invention and should not be construed as limiting the scope of the present invention, and that the insubstantial modifications and adaptations of the present invention by those skilled in the art based on the above disclosure are still within the scope of the present invention.

In addition, the raw materials used are commercially available from national chemical reagents, unless otherwise specified.